CN102274747B - Catalyst composition for preparing low-carbon olefin by using inferior oil and preparation method thereof - Google Patents
Catalyst composition for preparing low-carbon olefin by using inferior oil and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a catalyst composition suitable for preparing low-carbon olefin by using inferior oil and a preparation method thereof. The catalyst composition is characterized by consisting of two microspheres A and B, wherein the microsphere A is a shape-selecting cracking microsphere A consisting of 15-60wt% of ZSM-5 molecular sieve, 15-35wt% of silica sol in SiO2 and the balance of kaolin, and the wear strength of the microsphere A is not more than 2.0wt%; the microsphere B is a low-cost inferior oil conversion microsphere B consisting of 5-20wt% of Y molecular sieve, 10-30wt% of silica sol in SiO2, 0.5-5 wt% of pore forming agent and the balance of kaolin, the pore volume of the microsphere B is 0.1-0.5 ml/g, and the wear strength of the microsphere B is 2.5-4.5wt%; and the microspheres A and B are respectively shaped as a microsphere with a mean grain size of 50-80 microns by pulping and spray drying, and the adding proportions of the microspheres A and B are adjusted according to the run loss rate difference in the device so as to maintain the weight ratio of the microsphere A to the microsphere B of 1-(5: 1) in a system catalyst inventory. The composition is specifically suitable for the catalytic cracking/splitting process for fecundating low-carbon olefin by using inferior raw oil, and has the advantages of high low-carbon olefin yield, heavy metal pollution resistance and low catalyst consumption cost.
Description
Technical field
The present invention relates to the catalytic converting catalyst of petroleum hydrocarbon, specifically relate to a kind of carbon monoxide-olefin polymeric of under catalytic cracking/cracking condition, producing low-carbon alkene and preparation method thereof, belong to the petrochemical catalyst field from inferior feedstock oil.
Background technology
Low-carbon alkene such as ethene, propylene and butylene etc. are important Organic Chemicals, are used to make the raw material of polyolefin and the large chemical products of conduct production in a large number.Along with further developing of chemical industry and plastic product industry; Demand growth to low-carbon alkene is rapid; Developed the process route with paraffinic base vacuum gas oil (VGO) producing low-carbon alkene by catalytic pyrolysis, producing low-carbon alkene for heavy charge provides a valid approach and has obtained attention very.The technical process of typical producing low-carbon alkene by catalytic pyrolysis is as USP4980053, USP5670037, CN1102431, CN1085885A and USP6538169 etc. are described.
These catalytic pyrolysis processes and catalyst often have productivity of low carbon olefin hydrocarbon preferably when adopting the lighter paraffinic base vacuum gas oil (VGO) of high-quality and proportion.But along with oil more and more poor qualityization and heaviness; In the technical process of catalytic cracking/producing low-carbon olefins by cracking, will have to face the situation that adopts inferior and heavy and non-paraffin-base oil material; These poor qualities, heavy charge often than great, hydrogen-carbon ratio is low, the content of heavy metal vanadium, nickel is very high; Carboloy residue is also high; Disclosed these Deep Catalytic Cracking process processes of prior art and catalyst have just received considerable restraint, can occur in actual use that catalyst activity decay is fast, the agent consumption is high, olefins yield is low and the high situation of oil refining process cost.Propose to adopt in the prior art the way of catalytic pyrolysis again after the raw material hydrotreatment for this reason; Of CN100487080C, CN1333052C and USP6123830; But often cost is very high, investment is also big for hydrogenation process, and is that use in the technological reality of combination like this and few.Under non-hydroconversion condition, how to pass through to improve catalyst system; Make catalytic cracking/cracking technology process adapt to non-paraffinic base raw material better; Perhaps than method great, that hydrogen-carbon ratio is low, content of beary metal and the high inferior raw material of carboloy residue come low-carbon olefines high-output, report not still in the prior art.
The catalyst of low-carbon olefines high-output adopts composite oxide catalysts in early days, like USP3725495, USP3839485, SU550173, SU559946.Generally all contain the higher ZSM-5 molecular sieve of great amount of cost at present; As said at CN1117518, CN1222558A, CN1354224A, CN1230148A, CN1114916A, CN100537714C, CN1083092A and CN1272406C; Its effect is with being low-carbon alkene through the vapour after the cracking, diesel oil distillate second pyrolysis, and is of USP3758403, CN1043520A, USP500649, CN1026242C.In order to solve the not good problem of product selectivity of light olefin in the catalyst use; Reported the modification development of the ZSM-5 molecular sieve being carried out various complicacies in the prior art in a large number, like disclosed method in USP5236880, CN1205307, USP5380690, CN1114916A, CN1117518A, CN1143666A, CN1221015A, USP6342153, CN1222558A, USP6211104, CN1504540A.The catalytic cracking catalyst that also has has adopted expensive more molecular sieve active components such as Beta; Described in CN101134913A, CN1103105A, CN1057408A, CN1099788A, CN1145396A, CN1354224A, CN1504541A, CN1566275A and USP20050070422, but these measures make all that undoubtedly the cost of catalytic cracking catalyst is more high.Explored among the CN1100117C catalyst for cracking after using in the Deep Catalytic Cracking process process has been back to use in the catalytic cracking unit to improve the octane number of liquefied gas yield and gasoline in the catalytic cracking process, with the use cost of reduction catalyst again.
The report of relevant heavy-oil catalytic agent is very many in the prior art, generally all is used for the mink cell focus catalytic cracking process as major catalyst, does not report the Deep Catalytic Cracking process process that is used for low-carbon olefines high-output as cocatalyst.In order to keep the high activity of heavy-oil catalytic agent, in catalyst, mostly used a high proportion of high rare-earth content Y molecular sieve, of CN1733362, CN1733363, CN101386788, CN101385983 etc., cause it to cost an arm and a leg.In case the higher oil refining cost of catalytic cracking process that promptly brings of agent consumption significantly increases; Suppress the increase of oil refining cost so in manufacture process, all manage to increase its abrasion strength resistance with the depressant consumption, but this has increased the degree of heavy metal pollution of circulation in manufacture difficulty, cost and the use of catalyst undoubtedly again.The content that reduces Y molecular sieve undoubtedly can reduce the manufacturing cost of heavy oil transformation catalyst significantly, but this need manage to solve the low active not enough difficult problem of bringing of molecular sieve content.
Ludox is one type of good inorganic binder and low price, in the Cracking catalyst manufacture process, can be used as binding agent and uses and to reduce cost, as USP3867308 and USP3957689 are disclosed.But generally mostly be that being used for Cracking catalyst as additional adhesive with aluminium colloidal sol and/or boehmite binding agent prepares process, as USP4946814, CN100496711C, CN1552801A, CN1332765C, CN1312255C, CN1100847C are disclosed.Merely with Ludox as binding agent and kaolin is made the silicon substrate carrier Cracking catalyst such as the disclosed technology of CN1194072C is uncommon, Ludox, pore creating material and kaolin are improved heavy oil conversion performance as carrier and the technology that reduces cost is not seen in report as yet in the catalytic cracking catalyst of producing low-carbon alkene.
Along with the fast-developing cost of raw material of being brought of industrial economy is risen sharply; Requirement also must reduce catalyst buying and use cost in refining heavy, inferior raw material; In producing the catalytic cracking of low-carbon alkene/cracking technology process, how to make full use of expensive ZSM-5 molecular sieve active component and become the key that reduces the catalysis cost of use; The catalytic cracking catalyst of reporting in the prior art all is to be employed in that various active constituent elements such as compound ZSM-5, Y molecular sieve make catalyst form uniform way on the catalyst microsphere particle; Its shortcoming is the mismatch problem that can not solve two kinds of main active components well, fails to make full use of high value ZSM-5 molecular sieve structure and decay of activity relatively slowly and the characteristics of its pore passage structure tool anti-coking.Adopt the microsphere composition of two kinds of different molecular sieve active components and function; Run the flexible resize ratio of damage speed difference according to catalytic cracking/cracker condition of production and two kinds of microballoons; To adapt to poor oil raw material production low-carbon alkene technology and to alleviate heavy metal pollution and reduce the catalyst use cost, do not report in the prior art.
Summary of the invention
The objective of the invention is in order to solve existing deficiency in the prior art; Carbon monoxide-olefin polymeric of producing light olefins in a kind of poor oil catalytic cracking/cracking process and preparation method thereof is provided; Said low-carbon alkene is meant ethene, propylene and butylene; It is characterized in that this carbon monoxide-olefin polymeric is to be made up of two kinds of microballoons, wherein by 15～60 heavy %ZSM-5 molecular sieves, SiO
2What 15～35 heavy % Ludox and the surplus kaolin of meter constituted tear strength≤2.0 weight % selects shape cracking microballoon A; By 5～20 heavy %Y molecular sieves, SiO
210～30 heavy % Ludox of meter, 0.5～5 heavy % pore creating material and surplus kaolin constitute the microballoon of poor oil conversion cheaply B, and its pore volume is 0.1～0.5 milliliter/gram and tear strength 2.5～4.5 heavy %; A, B are the microballoon of 50～80 microns of average grain diameters through making beating, spray drying forming respectively; In catalytic cracking/cracking reaction device, run the ratio that the difference of decreasing speed is adjusted interpolation according to it, to keep A: the weight ratio of B in catalytic cracking/cracking reaction apparatus system catalyst inventory is 1～5: 1.
Selecting shape cracking microballoon A in the carbon monoxide-olefin polymeric of the said suitable poor oil producing light olefins of the present invention, is by 15～40 heavy %ZSM-5 molecular sieves, SiO under preferable case
220～30 heavy % Ludox and the surplus kaolin of meter constitute; Said ZSM-5 molecular screening is from HZSM-5, NH
4In ZSM-5, rare-earth type ZSM-5, phosphorous ZSM-5 and the phosphorous rare-earth type ZSM-5 molecular sieve one or more, these type ZSM 5 molecular sieves can be purchased acquisition; The said tear strength of selecting shape cracking microballoon A under preferable case≤1.6 heavy %; Because the ZSM-5 molecular sieve has better skeleton structure stability; And after the modification; Particularly phosphorus or rare earth modified after the ZSM-5 molecular sieve also have than the better activity stability of Y molecular sieve analog, and its unique three-dimensional open-framework coking and deactivation speed is much more slowly than the Y molecular sieve analog of supercage structure.The tear strength of selecting shape cracking microballoon A that will contain high value ZSM-5 molecular sieve is controlled in the preparation process in the better scope and decreases speed to reduce to run; What help to give full play to and utilize the ZSM-5 molecular sieve selects shape cracking function; Through reducing its consumption ratio in using, thereby reduce the use cost of whole catalyst in poor oil catalytic cracking/cracking process.
Poor oil cheaply in the carbon monoxide-olefin polymeric of the said suitable poor oil producing light olefins of the present invention transforms microballoon B, is by 8～15 heavy %Y molecular sieves, SiO under preferable case
215～25 heavy % Ludox of meter, 1～3 heavy % pore creating material and surplus kaolin constitute; Y molecular sieve well-known to those skilled in the art has constituted the Y molecular sieve of topmost manufacturing cost, particularly high rare-earth content in heavy oil/poor oil reforming catalyst.The content that reduces Y molecular sieve can reduce manufacturing, buying and the use cost of catalyst significantly; Y molecular sieve content is less than 15 heavy % in the present invention; Well below present catalytic cracking/catalyst for cracking the molecular sieve content of 30～40 heavy % that generally adopt, make that the cost of microballoon B is very low; Said Y molecular sieve is selected from HY, NH
4Among Y, Rare Earth Y, USY, rare earth USY, the rare earth HY one or more, these Y zeolites can be purchased acquisition.
The said pore creating material of the present invention is selected from one or more in magnesium lignosulfonate, carboxymethyl cellulose, the microcrystalline cellulose; All commercially available acquisition, adopting the prepared low-cost poor oil that goes out of pore creating material to transform the pore volume of microballoon B under preferable case is 0.2～0.4 milliliter/gram.The cracking that big pore volume helps heavy, component inferior transforms, and is not enough to remedy the low conversion capability that is caused of molecular sieve content, particularly under high reaction temperature, high agent-oil ratio condition; But also can carry easy coking components such as more colloid, asphalitine; Can the more heavy metal of enrichment behind the inactivation in catalytic cracking/cracking reaction; Thereby than the other a kind of catalytic component in the system; Select shape cracking microballoon A and have higher magnetic, help in the catalytic cracking/cracker that has magnetic separator unit (referring to CN1245482C), removing.Even do not attach in applied catalytic cracking/cracker the magnetic separator unit arranged; Because the prepared poor oil cheaply of preparation method of the present invention transforms the tear strength of microballoon B; Under preferable case, be controlled in the scope of 3.0～4.0 heavy %; The tear strength of selecting shape cracking microballoon A than high value is poor; Thereby and in its duct more its physical strength of coke destructible of enrichment; Cause it to run damage speed and select shape cracking microballoon A far above high value; It is different to form the replacement rate of two kinds of microballoons in catalytic cracking/cracking reaction apparatus system, makes to be difficult for selecting shape cracking microballoon A and can maintaining high ratio in the system catalyst reserve with very low replacement rate of coking and deactivation, and under preferable case, comprise and can keep A, the weight ratio A of two kinds of difference in functionality microballoons of B in catalytic cracking/cracker system catalyst reserve: B is 2～4: 1; Best catalysis efficiency is brought into play and the purpose of the shape selective catalysis lytic activity constituent element of protection high value thereby reach, and reduces total catalyst buying and use cost.
A, B in the said carbon monoxide-olefin polymeric of the present invention is to be the microballoon of 50～80 microns of average grain diameters through making beating, spray drying forming respectively, makes it can satisfy the requirement of carrying and using in the fluidizing reactor.Said making beating prepares process; Be each component raw material to be added to pull an oar in the colloid generating kettle according to the above ratio disperseed several hours; Also comprise the method for disperseing of grinding that adopts under the preferred condition; A in the carbon monoxide-olefin polymeric, B are processed into jelly respectively each component is fully disperseed, at the state that can on microspheres with solid, be evenly distributed behind the drying and moulding, so that bring into play catalysis efficiency and the wear strength that improves microballoon to greatest extent; The amount that in the preparation process, adds chemical water is not strict with; Said chemical water is meant through ion-exchange treatment and removes sodium ion, calcium ion and magnesium ion; Ion-exchange unit preparation through being purchased easily; The solid content that generally is control solid composite slurries in making beating preparation process is 20～45 heavy %; To make things convenient for making beating, conveying and spray drying forming, the solid content of preferred solid composite slurries is 25～35 heavy %, and its most of moisture is volatilized in spray-drying process; The spray drying forming of said A, B slurries adopts conventional method and condition; Be well known to those skilled in the art; General control spray tower exhaust temperature is 150～480 ℃; Atomisation pressure is to carry out under the condition of 50～60 atmospheric pressures, and preferably exhaust temperature is in 180～300 ℃ of scopes.
The inferior feedstock oil that the said carbon monoxide-olefin polymeric of the present invention is fit to is selected from one or more in reduced crude, decompression residuum, depressed heavy oil, wax tailings, propane deasphalting oil, the heavy oil.Refer in particular to those under the feedstock oil optimum condition of the present invention than great (0.91～0.94 grams per milliliter), content of beary metal high (nickel+vanadium 10～60 microgram/grams), carboloy residue high (3～6 heavy %) and the low inferior feedstock oil of hydrogen-carbon ratio.
When the said carbon monoxide-olefin polymeric of the present invention is used in the catalytic cracking/cracking process of inferior feedstock oil, comprise that the reaction temperature of device is general to adopt 480～620 ℃, under the optimum condition be 510～580 ℃; Oil ratio is 4～15, is 8～12 under the optimum condition; The steam that injects accounts for raw material 10～40 heavy %, is 15～30 heavy % under the optimum condition.The said carbon monoxide-olefin polymeric of the present invention regeneration temperature that the entering regenerator burns behind the reaction coking and deactivation is 670～750 ℃, and the regeneration temperature under preferable case is 690～720 ℃.
Catalytic cracking/catalyst for cracking with existing preparation low-carbon alkene is compared; The advantage of carbon monoxide-olefin polymeric provided by the present invention is that it can adapt to more that big proportion, hydrogen-carbon ratio are low, content of beary metal and the high inferior feedstock oil of carboloy residue, still can obtain high productivity of low carbon olefin hydrocarbon adopting under the inferior raw material oil condition.Carbon monoxide-olefin polymeric of the present invention has also solved two kinds of active component skeleton structures and the unmatched problem of decay of activity process effectively; Finally reach to make full use of and be worth the higher purpose of selecting shape lytic activity constituent element; Can low-carbon olefines high-output when not only in adopting the catalytic cracking/cracker of inferior feedstock oil, using; Preventing from heavy metal nickel, vanadium etc. have also reduced total manufacturing, buying and the use cost of catalyst to the pollution of system catalyst.
The specific embodiment
Come the present invention is done further explanation below in conjunction with embodiment, but therefore do not limit the present invention.
Tear strength is measured referring to " petrochemical industry analytical method (RIPP test method) ", and Yang Cui delimits the organizational structure, and nineteen ninety, Science Press published the standard method in the book; Pore volume is measured by the method for national standard (GB/T5816-1995); The particle diameter of particle adopts laser particle analyzer to measure; Other detects " oil and oil product test method national standard " referring to China Standard Press's publication in 1989.
Embodiment 1
With phosphorous HZSM-5 molecular sieve (industrial goods, Catalyst Factory, Nankai Univ, silica alumina ratio 30, the P of 300 grams
2O
53 heavy %) and 500 gram kaolin (industrial goods, Suzhou kaolin company) and 3 premium on currency be added in the colloid generating kettle making beating 30 minutes, (industrial goods, Qingdao City basic hundred million reaches silica gel chemical reagent work, SiO to add 1 liter of Ludox
225 heavy %) continue making beating after 10 minutes; With high shearing mixing emulsor (MBE-100L type; Shanghai Environmental Protection Equipment General Plant makes) the making beating homogeneous after 30 minutes in the laboratory with small-sized spray drier (LPG-5 type; Jianda Drying Equipment Co., Ltd., Changzhou's manufacturing) processes the microballoon A of embodiment 1 on, 65 microns of its average particulate diameters, tear strength 1.5 heavy %.
150 gram rare earth USY molecular sieves are (the same; Structure cell 2.455 nanometers; The heavy % of rare earth oxide 2.0), 600 gram kaolin (the same), 20 gram magnesium lignosulfonates (industrial goods, Tianjin leaf are chemical industry technology Co., Ltd now, 55 heavy %) 3 premium on currency and 1 liter of Ludox (the same) spray drying forming that uses the same method; Obtain the microballoon B of embodiment 1,0.3 milliliter/gram of pore volume, 69 microns of average particulate diameters, tear strength 3.5 heavy %.
Embodiment 2
The rare earth ZSM-5 molecular sieve that 250 grams are phosphorous (the same, silica alumina ratio 50, P
2O
52 heavy %; Rare earth oxide 2 heavy %), kaolin 550 grams (the same) and the making beating of 3 premium on currency are after 30 minutes; Add 1 liter of Ludox (the same) making beating after 10 minutes; Process embodiment 2 microballoon A, 62 microns of its average particulate diameters, tear strength 1.4 weight % in the laboratory on small-sized spray drier (the same) with high shearing mixing emulsor (the same) making beating homogeneous after 40 minutes.
130 gram USY molecular sieves are (the same; Structure cell 2.455 nanometers), 800 gram kaolin (the same), 20 gram carboxymethyl cellulose (industrial goods; Xinfeng, Dacheng County, Hebei province cellulose factory, purity 90%) 3 premium on currency and 1 liter of Ludox (the same) spray drying forming that uses the same method obtains the microballoon B of embodiment 2;, 0.28 milliliter/gram of pore volume, 67 microns of average particulate diameters, tear strength 3.9 heavy %.
Embodiment 3
With 140 gram NH
4ZSM-5 is (the same; Silica alumina ratio 25) and 140 gram rare earth ZSM-5 molecular sieves (the same; Silica alumina ratio 50), kaolin 550 grams (the same) and the making beating of 3 premium on currency are after 30 minutes; Add 1 liter of Ludox (the same) making beating after 15 minutes, process embodiment 3 microballoon A, 66 microns of its average particulate diameters, tear strength 1.5 weight % in the laboratory on small-sized spray drier (the same) after 50 minutes with high shearing mixing emulsor (the same) making beating homogeneous.
160 gram rare-earth Y molecular sieves are (the same; Rare earth oxide 16 heavy %), 1000 gram kaolin (the same), 20 gram microcrystalline cellulose (industrial goods; The bright biochemical technology Co., Ltd of protecting in Wuhan; 97%) 3 premium on currency and 1 liter of Ludox (the same) spray drying forming that uses the same method obtains the microballoon B of embodiment 3,0.29 milliliter/gram of pore volume, 66 microns of average particulate diameters, tear strength 3.8 heavy %.
Embodiment 4
250 gram HZSM-5 molecular sieves are (the same; Silica alumina ratio 25), kaolin 550 grams (the same) and the making beating of 3 premium on currency are after 30 minutes; Add 1 liter of Ludox (the same) making beating after 15 minutes in the colloid generating kettle; Process embodiment 4 microballoon A, 68 microns of its average particulate diameters, tear strength 1.5 weight % in the laboratory on small-sized spray drier (the same) with high shearing mixing emulsor (the same) making beating homogeneous after 30 minutes.
100 gram Rare Earth Y are (the same; The heavy % of rare earth oxide 16) with 40 to restrain HY (the same; Structure cell 2.460 nanometers) molecular sieve, 1000 gram kaolin (the same), 10 gram magnesium lignosulfonates (the same), 10 gram carboxymethyl celluloses (the same), 3 premium on currency and 1 liter of Ludox (the same) spray drying forming that uses the same method; Obtain the microballoon B of embodiment 4,0.30 milliliter/gram of pore volume, 67 microns of average particulate diameters, tear strength 3.6 heavy %.
Embodiment 5
Embodiment 1～4 is estimated embody technique effect of the present invention with small fixed flowing bed catalytic cracking unit (FFB-200 type, Huiersanji Green Chemical Science and Technology Co., Ltd., Beijing makes).Reaction raw materials oil is M100 fuel oil, and its main character is seen table 1.The feedstock oil that visible embodiment 5 is selected for use from table 1 belongs to all high inferior feedstock oil of big proportion, low hydrogen-carbon ratio, carbon residue and content of beary metal, generally could be as the raw material of Deep Catalytic Cracking process after the hydrotreatment of necessary process.
Table 1, feedstock oil character:
| Feedstock oil density, grams per liter | 932.1 | Content of vanadium, microgram/gram | 24.6 |
| Carbon, heavy % | 86.15 | Saturated hydrocarbons, heavy % | 52.4 |
| Hydrogen, heavy % | 11.68 | Aromatic hydrocarbons, heavy % | 32.7 |
| The feedstock oil carbon residue, heavy % | 5.4 | Colloid, heavy % | 14.6 |
| Nickel content, microgram/gram | 10.6 | Asphalitine, heavy % | 0.3 |
The condition of the reaction evaluating that table 2 carried out is: 560 ℃ of reaction temperatures, air speed 4 hours
-1, oil ratio 12, water filling 25 heavy %; Through 800 ℃, 100 heavy % steam aging 4 hours down, the weight ratio of microballoon A: B was 3: 1 in the catalyst for catalyst sample-loading amount 90 gram, catalyst, and this ratio is the ratio simulation reaches balancing run in Industrial Catalysis cracking/cracker after.
It is thus clear that adopting under the inferior feedstock oil situation shown in the table 1, carry out catalytic cracking/cracking reaction with the carbon monoxide-olefin polymeric of embodiment 1～4, still kept the productive rate of low-carbon alkenes such as higher ethene, propylene and butylene in its products distribution.
Table 2, main product distribute:
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Dry gas | 9.2 | 10.2 | 9.1 | 9.0 |
| Liquid hydrocarbon | 34.0 | 34.3 | 33.8 | 33.3 |
| Gasoline | 26.3 | 25.9 | 26.0 | 25.9 |
| Light oil | 14.1 | 13.8 | 14.3 | 14.9 |
| Heavy oil | 6.3 | 6.1 | 5.8 | 6.0 |
| Coke | 10.1 | 9.7 | 11.0 | 10.9 |
| Conversion ratio | 79.6 | 80.1 | 79.9 | 79.1 |
| Ethene | 3.1 | 3.9 | 3.7 | 2.9 |
| Propylene | 16.0 | 15.3 | 15.7 | 16.5 |
| Butylene | 11.1 | 10.9 | 11.0 | 11.2 |
Table 3 is cost situation that carbon monoxide-olefin polymeric of the present invention uses; As benchmark relatively, the use cost of the embodiment 1～4 that is carried out can find out that carbon monoxide-olefin polymeric of the present invention has also reduced the cost of use of catalyst when keeping poor oil low-carbon olefines high-output process in relatively with paraffinic base decompressed wax oil Deep Catalytic Cracking process under the Unit Weight charging and catalyst operating position.
The use cost situation of table 3, embodiment 1～4:
| Microballoon A during embodiment 1～4 carbon monoxide-olefin polymeric uses: the expendable weight ratio of microballoon B | 1∶2～3 |
| Paraffinic base decompressed wax oil Deep Catalytic Cracking process catalyst use cost, the ton charging | Benchmark |
| Embodiment 1～4 carbon monoxide-olefin polymeric adds up to use cost under the inferior feedstock oil, the ton charging | 80～90％ |
Need to prove at last; Above embodiment only is used to explain technical scheme of the present invention and is unrestricted; Although the present invention is specified with reference to preferred embodiment; Those of ordinary skill in the art should be appreciated that and can make amendment or be equal to replacement technical scheme of the present invention, and do not break away from the spirit and the scope of technical scheme of the present invention.
Claims (10)
1. the carbon monoxide-olefin polymeric of a suitable poor oil producing light olefins is characterized in that said composition is to be made up of two kinds of microballoons, wherein by 15～60 heavy %ZSM-5 molecular sieves, SiO
2What 15～35 heavy % Ludox and the surplus kaolin of meter constituted tear strength≤2.0 weight % selects shape cracking microballoon A; By 5～20 heavy %Y molecular sieves, SiO
210～30 heavy % Ludox of meter, 0.5～5 heavy % pore creating material and surplus kaolin constitute the microballoon of poor oil conversion cheaply B, and its pore volume is 0.1～0.5 milliliter/gram and tear strength 2.5～4.5 heavy %; A, B are the microballoon of 50～80 microns of average grain diameters through making beating, spray drying forming respectively; In catalytic cracking/cracking reaction device, run the ratio that the difference of decreasing speed is adjusted interpolation according to it, to keep A: the weight ratio of B in the system catalyst reserve is 1～5: 1.
2. the carbon monoxide-olefin polymeric of a kind of suitable poor oil producing light olefins according to claim 1 is characterized in that the said shape cracking microballoon A that selects is by 25～40 heavy %ZSM-5 molecular sieves, SiO
220～30 heavy % Ludox and the surplus kaolin of meter constitute.
3. the preparation method of the carbon monoxide-olefin polymeric of a kind of suitable poor oil producing light olefins according to claim 2 is characterized in that said ZSM-5 molecular screening one or more in HZSM-5, NH4ZSM-5, rare-earth type ZSM-5, phosphorous ZSM-5 and phosphorous rare-earth type ZSM-5 molecular sieve.
4. the carbon monoxide-olefin polymeric of a kind of suitable poor oil producing light olefins according to claim 1 is characterized in that the said heavy % in tear strength≤1.6 that selects shape cracking microballoon A.
5. the carbon monoxide-olefin polymeric of a kind of suitable poor oil producing light olefins according to claim 1 is characterized in that it is by 8～15 heavy %Y molecular sieves, SiO that said poor oil cheaply transforms microballoon B
215～25 heavy % Ludox of meter, 1～3 heavy % pore creating material and surplus kaolin constitute.
6. the preparation method of the carbon monoxide-olefin polymeric of a kind of suitable poor oil producing light olefins according to claim 5 is characterized in that said Y molecular sieve is selected from HY, NH
4Among Y, Rare Earth Y, USY, rare earth USY, the rare earth HY one or more.
7. the preparation method of the carbon monoxide-olefin polymeric of a kind of suitable poor oil producing light olefins according to claim 5 is characterized in that said pore creating material is selected from one or more in magnesium lignosulfonate, carboxymethyl cellulose, the microcrystalline cellulose.
8. the carbon monoxide-olefin polymeric of a kind of suitable poor oil producing light olefins according to claim 1 is characterized in that the pore volume that said low-cost poor oil transforms microballoon B is 0.2～0.4 a milliliter/gram.
9. the carbon monoxide-olefin polymeric of a kind of suitable poor oil producing light olefins according to claim 1 is characterized in that the tear strength that said low-cost poor oil transforms microballoon B is 3.0～4.0 heavy %.
10. the carbon monoxide-olefin polymeric of a kind of suitable poor oil producing light olefins according to claim 1, its method for using comprise keeps its weight ratio A in catalytic cracking/cracker system catalyst reserve: B is 2～4: 1.
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| CN101049571A (en) * | 2007-05-17 | 2007-10-10 | 南京工业大学 | Complex type molecular sieve catalysis, preparation method, and application in preparing crylic acid |
| CN101210190A (en) * | 2006-12-27 | 2008-07-02 | 中国石油化工股份有限公司 | Method for preparing low-carbon olefin and gasoline by synchronously feeding heavy petroleum hydrocarbon and methanol |
| EP2072604A1 (en) * | 2006-08-31 | 2009-06-24 | China Petroleum & Chemical Corporation | A process for catalytic converting hydrocarbons |
| CN102029177A (en) * | 2009-09-28 | 2011-04-27 | 中国石油化工股份有限公司 | Cracking catalyst and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP2072604A1 (en) * | 2006-08-31 | 2009-06-24 | China Petroleum & Chemical Corporation | A process for catalytic converting hydrocarbons |
| CN101210190A (en) * | 2006-12-27 | 2008-07-02 | 中国石油化工股份有限公司 | Method for preparing low-carbon olefin and gasoline by synchronously feeding heavy petroleum hydrocarbon and methanol |
| CN101049571A (en) * | 2007-05-17 | 2007-10-10 | 南京工业大学 | Complex type molecular sieve catalysis, preparation method, and application in preparing crylic acid |
| CN102029177A (en) * | 2009-09-28 | 2011-04-27 | 中国石油化工股份有限公司 | Cracking catalyst and preparation method thereof |
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Effective date of registration: 20170215 Address after: The three group of Jin Su Zhen Miao Er Cun, Wutongqiao District of Leshan City, Sichuan province 614800 Patentee after: Sichuan run and catalyze new materials Limited by Share Ltd Address before: 266500 Shandong City, Qingdao Province Economic and Technological Development Zone, Jiangshan Road, Jiangshan Rui garden, building 4, room 1, unit 401, room Patentee before: Zhuo Runsheng |
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Address after: 614000 group 3, Miaoer village, Jinsu Town, Wutongqiao District, Leshan City, Sichuan Province Patentee after: Runhe catalyst Co.,Ltd. Address before: 614800 group 3, Miaoer village, Jinsu Town, Wutongqiao District, Leshan City, Sichuan Province Patentee before: SICHUAN REZEL CATALYSTS NEW MATERIAL Co.,Ltd. |
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