CN103878019B - The catalytic cracking catalyst of isoparaffin gasoline is rich in volume increase - Google Patents
The catalytic cracking catalyst of isoparaffin gasoline is rich in volume increase Download PDFInfo
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- CN103878019B CN103878019B CN201410130865.XA CN201410130865A CN103878019B CN 103878019 B CN103878019 B CN 103878019B CN 201410130865 A CN201410130865 A CN 201410130865A CN 103878019 B CN103878019 B CN 103878019B
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Abstract
The present invention relates to a kind of catalytic cracking catalyst, the catalytic cracking catalyst of isoparaffin gasoline is rich in the volume increase of specifically reacting for catalytic cracking of petroleum hydrocarbon, be made up of according to parts by weight following raw material, USY molecular sieve 30 parts, auxiliary agent 5 ~ 15 parts, catalyst carrier 50 parts, binding agent 10 parts.Auxiliary agent is the silicoaluminophosphamolecular molecular sieves after silicoaluminophosphamolecular molecular sieves or citric acid-modified.Utilize the catalyst that this auxiliary agent is obtained, carry out macromolecule hydrocarbon cracking reaction, the gasoline component being rich in isoparaffin can be increased production, do not need to change existing equipment and Process ba-sis simultaneously.
Description
Technical field
The present invention relates to a kind of catalytic cracking catalyst, the catalytic cracking catalyst of isoparaffin gasoline is rich in the volume increase of specifically reacting for catalytic cracking of petroleum hydrocarbon.
Background technology
Isoparaffin, especially C4-C6 low-carbon (LC) isoparaffin, octane number is high, susceptibility is low, and having desirable volatility and burning episodic, is the ideal composition of gasoline.At present, catalytic cracking Olefin decrease technology, mainly through modulation catalytic cracking reaction, makes the olefines component wherein generated be further converted to alkane and aromatic hydrocarbons.The essence of this kind of catalyst is exactly add some hydrogen migration auxiliary agents, to improve the carrying out of the secondary response of catalytic cracking olefin substitute, reaches the object of Olefin decrease.
Cracking reaction mainly occurs in the bottom stage of riser reactor, and secondary response is mainly in the middle part of riser and top.Cracking reaction is endothermic process, and hydrogen migration, isomerization and aromatization are then exothermic process.Therefore, realize volume increase aromatization, isomerized products while reaction, first should regulate reaction temperature, as should high temperature bottom the riser in cracking reaction district, in the middle part of the riser in secondary response district, top then adopts relatively low temperature.Will there be enough time of staying in secondary response district, to ensure that the slower reaction of the reaction speeds such as isomerization, aromatisation and hydrogen migration is carried out.But the high temperature that these measures all generally adopt with current catalytic cracking unit, short contacting time operator scheme contradict.
Therefore to realize above-mentioned idea not changing on existing equipment and Process ba-sis, the catalytic component fully realizing isomerization, aromatisation and hydrogen transfer reaction under conscientiously can promoting high temperature, short contacting time condition must be developed, to solve above-mentioned contradiction.
Summary of the invention
For above-mentioned technical problem, the invention provides a kind of catalytic cracking catalyst strengthening isomerization reaction ability, under the effect of this catalyst, carry out macromolecule hydrocarbon cracking reaction, the gasoline component being rich in isoparaffin can be increased production, do not need to change existing equipment and Process ba-sis simultaneously.
The catalytic cracking catalyst of isoparaffin gasoline is rich in volume increase, is made up of, USY molecular sieve 30 parts, auxiliary agent 5 ~ 15 parts, catalyst carrier 50 parts, binding agent 10 parts following raw material according to parts by weight.
Wherein, auxiliary agent is the silicoaluminophosphamolecular molecular sieves with AEL pore passage structure;
Or auxiliary agent is the silicoaluminophosphamolecular molecular sieves with AEL pore passage structure after citric acid-modified.
The silicoaluminophosphamolecular molecular sieves with AEL pore passage structure adopted is SAPO-11 molecular sieve, and mesopore surface area accounts for more than 40% of the total specific area of this molecular sieve, is preferably more than 80%.
Catalyst carrier is kaolin, and binding agent is acidic silicasol.
Described auxiliary agent preparation method is:
(1) according to 1kgSAPO-11 molecular sieve: the ratio mixing of 1 ~ 10mol citric acid, at 23 ~ 100 DEG C of temperature, constant speed stirs, and the reaction time is 5 ~ 50 minutes;
(2) reaction terminate after, product is carried out suction filtration, washing, and at 100 DEG C dry 6h;
(3) after drying, product roasting at 550 DEG C, obtain having micropore, the distribution of mesoporous diplopore modification SAPO-11 molecular sieve as modification SAPO-11 molecular sieve auxiliary agent used in the present invention.
The preparation method that the catalytic cracking catalyst of isoparaffin gasoline is rich in volume increase is:
(1) USY molecular sieve, auxiliary agent, catalyst carrier, binding agent, with mix and blend 2h in water;
(2) mixture dry 3h at being placed in 110 DEG C, then through 700 DEG C of roasting 2h, heating rate 5 DEG C/min;
(3) material after roasting is ground, through 760 DEG C, obtain product after 100% steam burin-in process 4h.
The present invention designs from enhancing isomerization reaction ability angle catalytic cracking catalyst, adopts the SAPO-11 molecular sieve with the AEL pore passage structure of isomerization activity as auxiliary agent.Usually, the reaction of alkane isomerization on aluminium phosphate molecular sieve is considered to the result of Studies On The Shape-selective Catalysis, for low-carbon alkanes, mainly selects shape and transition state by product and selects shape two kinds of modes and form isohydrocarbon; And for long chain alkane, molecular size hinders its mass transfer in micropore canals, therefore select shape isomerization reaction by " aperture catalysis " and " key model ".But due to the aperture of micro porous molecular sieve less, the long chain alkane in heavy oil product is even difficult to enter very greatly at duct inner transmission matter resistance, and isomerization product or intermediate are lower by space constraint collateralization degree, and is difficult to effusion.Therefore, how can strengthen the isoversion performance of micropore SAPO-11 molecular sieve to large molecule alkane, becoming the present invention needs one of technical barrier solved.
The invention provides a kind of method of modifying of SAPO-11 molecular sieve, preparation has the auxiliary agent of modified molecular screen as catalyst of mesoporous-micropore double-pore structure.This modification SAPO-11 molecular sieve, there is superior low-carbon alkene, middle olefin skeletal isomerization ability, simultaneously, the flourishing mesoporous restriction that ensure that diffusion couple isomerization reaction under catalytic cracking condition, isomerization reactions can be promoted from reacting, spreading two aspects, improve catalytically cracked gasoline composition.This molecular sieve is also easy to be scattered in catalytic cracking matrix, is easy to compound with existing catalytic cracking catalyst active component.Utilize the catalyst that this auxiliary agent is obtained, carry out macromolecule hydrocarbon cracking reaction, the gasoline component being rich in isoparaffin can be increased production, do not need to change existing equipment and Process ba-sis simultaneously.
Specific embodiment
The following examples will be described further feature of the present invention, but protection scope of the present invention is not by the restriction of these embodiments.
The method of testing related in embodiment is:
The specific area of auxiliary agent SAPO-11 molecular sieve or modification SAPO-11 molecular sieve, the assay method of pore volume are: low-temperature nitrogen adsorption method.Adopt the multi-functional adsorption instrument of TriStar3000 type that Micromeritics company of the U.S. produces.Sample is more than vacuum pre-treatment 3h at 300 DEG C first, to remove adsorption impurity and moisture; With high-purity N
2as adsorbate, at liquid nitrogen 77K temperature, measure Adsorption and desorption isotherms.Calculate total specific area of molecular screen material with BET method, calculate microcellular structure specific area and pore volume with t-plot method, calculate specific area and the pore volume size of meso-hole structure with BJHDesorption method, and make its graph of pore diameter distribution according to result.
Micro-activity is evaluated, and namely MA evaluates, and adopts ASTM-D3907 method.Catalyst in advance 760 DEG C, process 4h under 100% water vapour condition, using grand celebration straight-run gas oil and wax tailings as reaction raw materials oil, reaction temperature 500 DEG C, the average inlet amount 1.0g of feedstock oil oil, oil ratio is 3.
The raw material used in embodiment and specification:
SAPO-11 molecular sieve: technical grade, Nankai's catalyst plant;
Citric acid: analyze pure, Chemical Reagent Co., Ltd., Sinopharm Group;
Ludox: technical grade, Qingdao Marine Chemical Co., Ltd.;
USY molecular sieve: technical grade, Lanzhou catalyst plant;
Kaolin: technical grade, Zibo Hua Qing powder body material scientific & technical corporation.
Embodiment 1:
Adopt SAPO-11 molecular sieve, be designated as 1# auxiliary agent.
Embodiment 2:
Take 10gSAPO-11 molecular sieve, and the citric acid solution measuring 100mL is as inorganic agent.SAPO-11 molecular sieve and inorganic agent are added successively in round-bottomed flask, at being placed in 40 DEG C, constant speed stirs.Question response is after 30 minutes, stops stirring, and product in flask is carried out suction filtration, washing, and at 100 DEG C dry 6h, roasting at 550 DEG C, obtains auxiliary agent afterwards.
The concentration of the citric acid solution adopted in the present embodiment is respectively 0.1mol/L, 0.25mol/L, 0.5mol/L, 0.75mol/L and 1.0mol/L, and the auxiliary agent obtained by the citric acid solution of variable concentrations is designated as 2# auxiliary agent, 3# auxiliary agent, 4# auxiliary agent, 5# auxiliary agent and 6# auxiliary agent successively.
The hole structural property of auxiliary agent is obtained in table 1 through different citric acid concentration process for embodiment 1 and embodiment 2.
The different citric acid concentration of table 1 prepares the hole structural property of meso-SAPO-11
Embodiment 3:
Take 10gSAPO-11 molecular sieve, and measure the citric acid treatment agent of the 0.5mol/L of 100mL.SAPO-11 molecular sieve and inorganic agent are added successively in round-bottomed flask, constant speed of heating stirs.Question response is after 30 minutes, stops stirring, and product in flask is carried out suction filtration, washing, and at 100 DEG C dry 6h, roasting at 550 DEG C, obtains auxiliary agent afterwards.
The temperature of heating adopted in the present embodiment is respectively 23 DEG C, 60 DEG C, 80 DEG C and 100 DEG C, and the auxiliary agent of obtained 2 is designated as 7# auxiliary agent, 8# auxiliary agent, 9# auxiliary agent and 10# auxiliary agent respectively.The hole structural property of each auxiliary agent is in table 2.
The different citric acid treatment temperature of table 2 prepares the hole structural property of meso-SAPO-11
Embodiment 4:
Take 10gSAPO-11 molecular sieve, and measure the citric acid treatment agent of the 0.5mol/L of 100mL.SAPO-11 molecular sieve and inorganic agent are added successively in round-bottomed flask, at being placed in 40 DEG C, constant speed stirs.After question response certain hour, stop stir, product in flask is carried out suction filtration, washing, and at 100 DEG C dry 6h, roasting at 550 DEG C, obtains auxiliary agent afterwards.
The reaction time adopted in the present embodiment is respectively 5 minutes, 10 minutes, 20 minutes and 50 minutes, and obtained auxiliary agent is designated as 11# auxiliary agent, 12# auxiliary agent, 13# auxiliary agent and 14# auxiliary agent respectively.
The hole structural property measurement result of the auxiliary agent that the present embodiment obtains is in table 3
The table 3 different citric acid treatment time prepares the hole structural property of meso-SAPO-11
Embodiment 5:
Raw material takes according to parts by weight, USY molecular sieve 30 parts, auxiliary agent 10 parts, catalyst carrier 50 parts, binding agent 10 parts.Auxiliary agent is the 1# auxiliary agent of embodiment 1, using kaolin as catalyst carrier, acidic silicasol as binding agent, mix and blend 2h in water.At being placed in 110 DEG C after dry 3h, roasting 2h at 700 DEG C, heating rate 5 DEG C/min.Product being ground, through obtaining catalyst sample after 100% steam burin-in process 4h at 760 DEG C, being designated as 1# catalyst.
Embodiment 6:
Raw material takes according to parts by weight, USY molecular sieve 30 parts, auxiliary agent 10 parts, catalyst carrier 50 parts, binding agent 10 parts.Auxiliary agent is the 2# auxiliary agent of embodiment 2, using kaolin as catalyst carrier, acidic silicasol as binding agent, mix and blend 2h in water.At being placed in 110 DEG C after dry 3h, roasting 2h at 700 DEG C, heating rate 5 DEG C/min.Product being ground, through obtaining catalyst sample after 100% steam burin-in process 4h at 760 DEG C, being designated as 2# catalyst.
Comparative example 1:
Raw material takes according to parts by weight, USY molecular sieve 30 parts, catalyst carrier 60 parts, binding agent 10 parts.Do not make used additives, using kaolin as catalyst carrier, acidic silicasol as binding agent, mix and blend 2h in water.At being placed in 110 DEG C after dry 3h, roasting 2h at 700 DEG C, heating rate 5 DEG C/min.Product being ground, through obtaining catalyst sample after 100% steam burin-in process 4h at 760 DEG C, being designated as 1# contrast medium.
Embodiment 7:
The present embodiment adopts the micro-activity of RFCC micro-reactor to 1# catalyst, 2# catalyst and 1# contrast medium that embodiment 5, embodiment 6 and comparative example 1 are synthesized to evaluate.Feedstock oil adopts grand celebration straight-run gas oil.Concrete operation step is as follows:
1# contrast medium, 1# catalyst, 2# catalyst, respectively through after compression molding, are crushed to 80-180 order, take 3g and load minisize reaction pipe, and fill up and down with quartz sand.Be warming up to 500 DEG C, carry out weight demarcation with micro-injection pump to reaction oil product, in course of reaction, pump into about 1.0g straight-run gas oil or wax tailings carry out catalytic cracking reaction.Liquid-phase product is by ice-water bath condensation, and gas-phase product is collected in airbag, and gas flow is calculated by reaction pressure water number.
For the catalytic cracking reaction evaluation result of 1# contrast medium, 1# catalyst, 2# catalyst in table 4.
Table 4 straight-run gas oil catalytic cracking reaction performance evaluation
ISG: isomerization product composition in gasoline products.
Embodiment 11:
The present embodiment adopts the micro-activity of RFCC micro-reactor to 1# catalyst, 2# catalyst and 1# contrast medium that embodiment 5, embodiment 6 and comparative example 1 are synthesized to evaluate.Feedstock oil adopts grand celebration wax tailings.Concrete operation step is as follows:
1# contrast medium, 1# catalyst, 2# catalyst, respectively through after compression molding, are crushed to 80-180 order, take 3g and load minisize reaction pipe, and fill up and down with quartz sand.Be warming up to 500 DEG C, carry out weight demarcation with micro-injection pump to reaction oil product, in course of reaction, pump into about 1.0g straight-run gas oil or wax tailings carry out catalytic cracking reaction.Liquid-phase product is by ice-water bath condensation, and gas-phase product is collected in airbag, and gas flow is calculated by reaction pressure water number.
For the catalytic cracking reaction evaluation result of 1# contrast medium, 1# catalyst, 2# catalyst in table 5.
Table 5 wax tailings catalytic cracking reaction performance evaluation
ISG: isomerization product composition in gasoline products.
Claims (1)
1. the catalytic cracking catalyst of isoparaffin gasoline is rich in volume increase, it is characterized in that: be made up of according to parts by weight following raw material, USY molecular sieve 30 parts, auxiliary agent 5 ~ 15 parts, catalyst carrier 50 parts, binding agent 10 parts; Described auxiliary agent is the silicoaluminophosphamolecular molecular sieves after citric acid-modified; Described silicoaluminophosphamolecular molecular sieves is SAPO-11 molecular sieve, and mesopore surface area accounts for more than 40% of the total specific area of this molecular sieve.
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