CN104888840A - Preparation method for high-framework silica-alumina-ratio in-situ crystallization FCC heavy oil transforming auxiliary agent - Google Patents
Preparation method for high-framework silica-alumina-ratio in-situ crystallization FCC heavy oil transforming auxiliary agent Download PDFInfo
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Abstract
The invention discloses a preparation method for a high-framework silica-alumina-ratio in-situ crystallization FCC heavy oil transforming auxiliary agent. The method comprises: pulping and dispersing kaolin and natural diatomite to prepare serosity, adding a dispersing agent, and performing spray drying and forming so as to obtain parent microspheres; sequentially adding sodium silicate, deionized water, NaOH, a guiding agent, GM and PM in proportion into a crystallization reaction kettle, and performing hydrothermal crystallization so as to obtain crystallization products; exchanging the crystallization products through an inorganic ammonium salt solution, and performing filtration and washing so as to obtain first exchange materials and second exchange materials; roasting the second exchange materials so as to obtain first roasting materials; performing ion exchange on the roasting materials through a rare earth solution, and performing filtration, washing and re-filtration so as to obtain third exchange materials; roasting the third exchange materials so as to obtain second roasting materials; performing liquid-phase aluminum extraction and silicon supplement on the second roasting materials through a fluorine-silicon acid solution, and performing filtration, washing and drying so as to obtain the required heavy oil transforming auxiliary agent.
Description
Technical field
The present invention relates to a kind of catalytic cracking (Fluid Catalytic Cracking, FCC) preparation method of heavy oil transformation auxiliary agent, more particularly, a kind of raising catalytically cracked gasoline yield is related to, the preparation method of high framework si-al ratio in-situ crystallization heavy oil transformation auxiliary agent.
Background technology
Along with world's crude oil in poor quality day by day, catalytically cracked material character is also deteriorated increasingly.The heavy metal pollution performances such as this residual oil cracking performance to FCC catalyst, coke selectivity and anti-Ni, V are had higher requirement.Meanwhile, improving FCC gasoline yield is the important technology road warp that current oil refining enterprise promotes economic benefit.And the gasoline selective improving FCC catalyst improves one of the most effective technological means of FCC gasoline yield.
Current FCC catalyst is mainly divided into conventional semi-synthetic y-type zeolite catalyst and in-situ crystallization y-type zeolite catalyst.Conventional semi-synthetic FCC catalyst preparation technology normally first prepares y-type zeolite active component, is then mixed with the matrix components containing natural clay and binding agent by the y-type zeolite of modification, makes micro-spherical catalyst by spray drying forming.In-situ crystallization y-type zeolite catalyst, generally take kaolin as raw material, at high temperature roasting after spray shaping, kaolin microsphere through roasting is provided with good abrasion resistance properties, then carry out in-situ crystallization in the basic conditions, in kaolin part Silicified breccias source from microballoon by extracting to microballoon and channel surfaces, and then at microballoon duct inwall and Surface Creation y-type zeolite crystal, and in microballoon, remaining silicon and aluminum source is present in microballoon as matrix.Compared with the semi-synthetic FCC catalyst of routine, in-situ crystallization FCC catalyst has the advantages such as good hydrothermal stability, heavy oil conversion performance and preventing from heavy metal ability are strong.
The technology in early stage of in-situ crystallization synthesis y-type zeolite generally adopts powdery y-type zeolite to grow to impel the crystallization of Y phase zeolite as crystal seed.Current kaolin microsphere in-situ crystallization technology more trends towards adopting directed agents to induce crystallization and the growth of y-type zeolite on microballoon.Directed agents induction mode is more conducive to making synthetic product have higher degree of crystallinity and better anti-wear performance than crystal seed revulsion.
In FCC process, can large molecule heavy oil enter that catalyst duct contacts with Active sites is the Molecular Cloning greatly key of heavy oil.In-situ crystallization catalyst is compared with the semi-synthetic FCC catalyst of routine, why there is better heavy oil conversion performance, basic reason is that the zeolite activity component of in-situ crystallization catalyst is the hole surface nanoscale ground growth in situ at carrier, allow active component be exposed to channel surfaces to greatest extent, thus significantly improve the accessibility in activated centre.
Can not directly be used as FCC catalyst or heavy oil transformation auxiliary agent containing NaY zeolite crystallization product synthesized by kaolin in-situ crystallization, but through repeatedly ammonium and/or rare-earth cation exchange, modification by calcination, the most Na in zeolite will be removed
+afterwards, could as FCC catalyst or heavy oil transformation auxiliary agent.But gas phase takes off the humidity that sodium aluminium-eliminating and silicon-replenishing technical process requires strictly to control in-situ crystallization product before modified, is easy to occur SiCl in modifying process
4leakage accident, controls difficulty very large, is difficult to implement industrialization, and can increases the manufacturing cost of catalyst by a relatively large margin.
Make a general survey of that in-situ crystallization prepares FCC catalyst, the prior art of auxiliary agent is not difficult and find, adopt conventional in situ crystallization and the FCC catalyst prepared by cation exchange technology, auxiliary agents of silicon aluminum ratio lower, General N aY skeleton SiO
2/ Al
2o
3mol ratio is lower than 5.4, and thus the hydrothermal stability of catalyst and coke selectivity remain to be further improved.Simultaneously because of the skeleton SiO of kaolin starting material itself
2/ Al
2o
3mol ratio lower (close to 1), causes sodium metasilicate needed for in-situ crystallization technology/kaolin ratio high.Although add the compound that adding molecular organic additive or decomposition temperature or boiling point be less than 150 DEG C can optimize in-situ crystallization product pore structure in kaolin spray shaping process, the abrasion resistance properties of catalyst is often caused to be deteriorated.Use SiCl
4gas carries out gas phase to kaolin in-situ crystallization product and takes off the modification of sodium aluminium-eliminating and silicon-replenishing, can improve in-situ crystallization product framework si-al ratio, but can not optimize in-situ crystallization product pore structure, and to in-situ crystallization product humidity requirement is very high before modified, easily occur SiCl
4leakage accident, controls difficulty very large, is difficult to implement industrialization, also increases the manufacturing cost of catalyst by a relatively large margin.
Summary of the invention
The object of the invention is the shortcoming overcoming prior art, a kind of preparation method of high framework si-al ratio in-situ crystallization FCC heavy oil transformation auxiliary agent is provided, FCC heavy oil transformation auxiliary agent prepared by the inventive method is used in FCC process, heavy oil conversion performance and the coke selectivity of conventional FCC catalyst can not only be improved, the yield of FCC gasoline can be significantly improved simultaneously.
The preparation method of high framework si-al ratio in-situ crystallization FCC heavy oil transformation auxiliary agent provided by the present invention includes the step one of crystallization product and the step 2 of preparation FCC heavy oil transformation auxiliary agent; To concrete step be described in detail below:
Step one: prepared by crystallization product
Step 11, protokaolin and natural diatomaceous earth are dropped in water in proportion, the slurries of solid content 30 ~ 50 weight portion % are made in making beating dispersion, dispersant is added in slurries, spray drying forming is the parent microballoon of 20 ~ 110 microns, wherein more than 90% is 40 ~ 100 microns, described spray drying tower inlet temperature 550 ~ 700 DEG C, outlet temperature 150 ~ 300 DEG C; Described dispersant comprises sodium metasilicate, NaOH, sodium pyrophosphate, calgon, and its addition is 2.0 ~ 4.0 weight portion % of natural diatomaceous earth and kaolin total amount.
Natural diatomaceous earth described in a step 11 and kaolinic weight ratio are 1: 1 ~ 1: 20, are preferably 1: 3 ~ 1: 15.
Described natural diatomaceous earth is particle diameter≤2.0 micron after ball mill ball milling, its SiO
2>=80 weight portion %, Fe
2o
3≤ 1.5 weight portion %, K
2o+Na
2o≤1.0 weight portion %;
Described kaolin comprises soft kaolin, hard Raolinite, gangue, wherein particle diameter 2.5 ~ 3.5 microns, crystal kaolinite content>=80 weight portion %, quartz≤1.0 weight portion %, Fe
2o
3≤ 1.7 weight portion %, K
2o+Na
2o≤0.5 weight portion %.
Step 12, part parent microballoon, at 940 ~ 1000 DEG C of roasting temperature 1 ~ 3h, to change into based on spinelle and with the height soil microballoon GM of a small amount of mullite, another part, at 650 ~ 900 DEG C of roasting temperature 1 ~ 3h, changes into partially native microballoon PM;
Containing mullite 3.0 ~ 15 weight portion % in GM microballoon described in step 12, its abrasion index is less than 4%/h; Described PM microballoon is not containing mullite, and its abrasion index is less than 4%/h.
Step 13, sodium metasilicate, deionized water, NaOH, directed agents, GM, PM are added in crystallization still in proportion successively, in 90 ~ 98 DEG C of hydrothermal crystallizings 16 ~ 32 hours under stirring, cross and filter mother liquor, filter cake spends deionized water to cleaning solution pH value less than 10.5, obtains NaY zeolite content 30 ~ 65 weight portion %, zeolitic frameworks SiO after filtration
2/ Al
2o
3the crystallization product JH of moles 4.5 ~ 5.5; Stirring condition is 150 revs/min ~ 600 revs/min;
Described directed agents constitutive molar ratio is (14 ~ 16) SiO
2: (0.7 ~ 1.3) Al
2o
3: (14 ~ 16) Na
2o: (300 ~ 330) H
2o.
The weight ratio of the sodium metasilicate described in step 13, deionized water, NaOH, directed agents, GM, PM: GM/PM=10: 0 ~ 4: 6; Liquid phase SiO
2/ (GM+PM)=0.4 ~ 2.0.The mass percent concentration of described NaOH is 14 ~ 18%.
Step 2: prepared by FCC heavy oil transformation auxiliary agent
Step 21, crystallization product JH inorganic ammonium salt solution step one obtained exchanges, inorganic ammonium salt/JH weight ratio 0.2 ~ 0.5, give-and-take conditions: PH 3.0 ~ 3.5, temperature 90 ~ 95 DEG C, time 0.5 ~ 1h, through filtering, washing and to obtain a friendship material after exchange;
In step 21, said inorganic ammonium salt is selected from one or more combinations in interior inorganic ammonium salt of ammonium chloride, ammonium sulfate, ammonium nitrate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), ammonium phosphate, ammonium phosphite, dihydrogen phosphite ammonium, ammonium acetate, ammonium formate.
Step 22, one hands over material to use the solution containing rare-earth salts to carry out ion-exchange, give-and-take conditions: PH 3.5 ~ 4.0, temperature 90 ~ 95 DEG C, time 0.5 ~ 1h, through filtration, washing after exchange, refilters, and 120 DEG C are dry that two friendships are expected;
Step 23, two hand over material roasting 1 ~ 2h at 550 ~ 600 DEG C, obtain a roasting material;
Step 24, the solution of a roasting material containing rare-earth salts carries out ion-exchange, give-and-take conditions again: PH 3.5 ~ 4.0, temperature 90 ~ 95 DEG C, time 0.5 ~ 1h, through filtration, washing after exchange, refilter, obtain three friendship material;
In step 22, step 24, said rare-earth salts refers to the rare-earth salts for zeolite rare earth exchanged well known to those skilled in the art, is generally be key component with lanthanum and/or cerium chloride, nitrate or sulfate; Wherein the content (with oxide basis) of lanthanum and/or cerium is greater than 50 weight portion %, is preferably greater than 60 weight portion %, more preferably greater than 70 weight portion %.
Step 25, three hand over material roasting 1 ~ 2h at 550 ~ 650 DEG C, obtain two roasting material;
Step 26, two roasting material are carried out the reaction of liquid phase aluminium-eliminating and silicon-replenishing with the solution of fluorine-containing silicic acid, and the addition of described fluosilicic acid is 1 ~ 30% of two roasting material weight, is preferably 5 ~ 20% of two roasting material weight.Then filter, wash, be drying to obtain required heavy oil transformation auxiliary agent, its Re
2o
3content is 0.5 ~ 8.0 weight portion %, NaY zeolite content 30 ~ 65 weight portion %, zeolitic frameworks SiO
2/ Al
2o
3moles 5.6 ~ 20, Na
2o≤0.4 weight portion %.
Said silicate fluoride solution joins in the slurries of zeolite within the time of 5 ~ 30 minutes, preferably 10 ~ 20 minute in step 26, then reacts more than 0.5 hour at 50 ~ 90 DEG C, is preferably 0.5 ~ 2 hour.
FCC heavy oil transformation auxiliary agent preparation method provided by the invention has following characteristics:
(1) use the kaolin in diatomite Some substitute GM and PM of Silicon-rich in crystallization product preparation process, improve the SiO of in-situ crystallization raw material greatly
2/ Al
2o
3mol ratio, reduces sodium metasilicate needed for in-situ crystallization/kaolin ratio, reduces the difficulty of crystallization, reduce the discharge capacity of Si and Na in crystallization mother liquor simultaneously.
(2) two roasting material adopt fluosilicic acid to carry out chemical aluminium-eliminating and silicon-replenishing modification, and be effectively stripped of Na and the non-framework aluminum of y-type zeolite in crystallization product on the one hand, add mesoporous amount, the accessibility of zeolite improves, meanwhile, and zeolitic frameworks SiO
2/ Al
2o
3mol ratio can be increased to more than 10, and degree of crystallinity degree is not suffered a loss.
(3) two roasting material adopt fluosilicic acid to carry out the modification of chemical aluminium-eliminating and silicon-replenishing method, substitute ammonium salt and exchange de-Na, reduce ammonium nitrogen discharged.
FCC heavy oil transformation auxiliary agent prepared by the inventive method is used for, in FCC process, can not only improving heavy oil conversion performance and the coke selectivity of conventional FCC catalyst, can significantly improve the yield of FCC gasoline simultaneously.
Detailed description of the invention
The following examples will be further described the present invention, but not thereby limit the present invention.
The Na of sample prepared in each embodiment and comparative example
2o content is by aas determination; Re
2o
3, Al
2o
3and SiO
2content is by x-ray fluorescence spectrometry; Zeolitic frameworks SiO
2/ Al
2o
3mol ratio and NaY content by X-ray diffraction method (XRD) adopt RIPP 145-90 standard method (see " Petrochemical Engineering Analysis method (RIPP test method) ", the volumes such as Yang Cuiding, Science Press, nineteen ninety version) measure; Specific area, pore volume are measured by standard BET method.
In embodiments of the invention and comparative example, diatomite is the powdery natural diatomaceous earth that Changbai Mountain, Linjiang city filter aid Co., Ltd produces, and primary chemical composition is in table 1.Kaolin is the special kaolin of Cracking catalyst that Kaolin of Suzhou company produces, and it is mainly Na
2the quartz sand of O and < 0.8 weight portion %.Sodium silicate solution is the industrial products of Ju Li get Chemical Co., Ltd., SiO
2content is 250g/l, Na
2o content 88g/l.Chlorination mishmetal is Inner Mongol Baotou rare earth company industrial products, RE
2o
3content 46 weight portion %, RE
2o
3consist of La
2o
353.2 weight portion %, CeO
213.0 weight portion %, Pr
6o
1113.0 weight portion %, Nd
2o
320.8 weight portion %.Sodium hydroxide solution is that Beijing flies sharp roc and reaches Nacl and sell Co., Ltd industrial products, and NaOH content is 14 weight portion %.The industrial products of high alkali deflection aluminium acid sodium solution Ju Li get Chemical Co., Ltd., Al
2o
3content is 42g/l, Na
2o content 280g/l.
In the present invention, embodiment 1 ~ 10 is the preparation of in-situ crystallization microballoon.
embodiment 1
200 kilograms of (butt) natural diatomaceous earths and 200 kilograms of decationizing water are dropped into volume 1m
3vertical ball mill in ball milling 30 minutes, make the natural diatomaceous earth slurries of solid content 50%, natural diatomaceous earth particle diameter D (v, 0.5) 1.6 microns, for subsequent use.
By natural diatomaceous earth and protokaolin in natural diatomaceous earth (butt): the ratio of protokaolin (butt)=1: 4 drops in stirred tank, the making beating dispersion that adds water makes the slurries that solid content is 35 weight portion %, natural diatomaceous earth and protokaolin butt gross weight 50 kilograms in slurries.In slurries, add the sodium metasilicate (relative to diatomite and protokaolin butt gross weight) of 2 weight portion % as dispersant, spray drying forming, obtains 48 kilograms of parent microballoons.
Get 3 kilograms of parent microballoons roasting 3h at 940 DEG C in Muffle furnace, to change into based on spinelle and with the height soil microballoon GM of a small amount of mullite, 3 kilograms of parent microballoons, at 870 DEG C of roasting temperature 1h, change into partially native microballoon PM.
Successively by sodium metasilicate (SiO under stirring (300 revs/min)
2250g/l, Na
2o 88g/l) 1300ml, 14% NaOH solution 600ml, directed agents (SiO
2: Al
2o
3: Na
2o: H
2o mol ratio=15: 1: 16: 320) 80ml, deionized water 300ml, GM600 gram, PM400 gram drop in stainless steel cauldron, are warming up to 92 DEG C and thermostatic crystallization 24 hours.Crystallization terminates rear mistake and filters mother liquor, and filter cake spends deionized water to cleaning solution pH value less than 10.5, obtains NaY zeolite content 32 weight portion %, zeolitic frameworks SiO after filtration
2/ Al
2o
3the crystallization product JH of moles 5.0
01.
embodiment 2
Get 3 kilograms of parent microballoons roasting 1h at 990 DEG C in Muffle furnace, to change into based on spinelle and with the height soil microballoon GM of a small amount of mullite, 3 kilograms of parent microballoons, at 870 DEG C of roasting temperature 1h, change into partially native microballoon PM.
To stir under (150 revs/min) and successively sodium metasilicate 3800ml, NaOH solution 500ml, directed agents 200ml, GM300 gram, PM300 gram are dropped in stainless steel cauldron, be warming up to 92 DEG C and thermostatic crystallization 20 hours.Crystallization terminates rear mistake and filters mother liquor, and filter cake spends deionized water to cleaning solution pH value less than 10.5, obtains NaY zeolite content 42 weight portion %, zeolitic frameworks SiO after filtration
2/ Al
2o
3the crystallization product JH of moles 4.8
02.
embodiment 3
Get 3 kilograms of parent microballoons roasting 3h at 940 DEG C in Muffle furnace, to change into based on spinelle and with the height soil microballoon GM of a small amount of mullite, 3 kilograms of parent microballoons, at 730 DEG C of roasting temperature 3h, change into partially native microballoon PM.
To stir under (180 revs/min) and successively sodium metasilicate 3300ml, NaOH solution 450ml, directed agents 100ml, GM160 gram, PM340 gram are dropped in stainless steel cauldron, be warming up to 92 DEG C and thermostatic crystallization 32 hours.Crystallization terminates rear mistake and filters mother liquor, and filter cake spends deionized water to cleaning solution pH value less than 10.5, obtains NaY zeolite content 38 weight portion %, zeolitic frameworks SiO after filtration
2/ Al
2o
3the crystallization product JH of moles 4.6
03.
embodiment 4
Get 3 kilograms of parent microballoons at 870 DEG C of roasting temperature 1h, change into partially native microballoon PM.
Stir under (450 revs/min) and successively sodium metasilicate 3000ml, NaOH solution 180ml, directed agents 200ml, deionized water 50ml, PM140 gram are dropped in stainless steel cauldron, be warming up to 92 DEG C and thermostatic crystallization 24 hours.Crystallization terminates rear mistake and filters mother liquor, and filter cake spends deionized water to cleaning solution pH value less than 10.5, obtains NaY zeolite content 65 weight portion %, zeolitic frameworks SiO after filtration
2/ Al
2o
3the crystallization product JH of moles 5.1
04.
embodiment 5
To stir under (250 revs/min) and successively sodium metasilicate 6200ml, NaOH solution 350ml described in example 1, directed agents 200ml, deionized water 25ml, GM560 gram, PM140 gram are dropped in stainless steel cauldron, be warming up to 92 DEG C and thermostatic crystallization 28 hours.Crystallization terminates rear mistake and filters mother liquor, and filter cake spends deionized water to cleaning solution pH value less than 10.5, obtains NaY zeolite content 35 weight portion %, zeolitic frameworks SiO after filtration
2/ Al
2o
3the crystallization product JH of moles 5.4
05.
embodiment 6
Get 3 kilograms of parent microballoons roasting 3h at 940 DEG C in Muffle furnace, to change into based on spinelle and with the height soil microballoon GM of a small amount of mullite, 3 kilograms of parent microballoons, at 800 DEG C of roasting temperature 1h, change into partially native microballoon PM.
To stir under (180 revs/min) successively by sodium metasilicate 2000ml, 14% NaOH solution 1300ml, directed agents 180ml, deionized water 100ml, GM480 gram, PM120 gram drop in stainless steel cauldron, be warming up to 92 DEG C and thermostatic crystallization 28 hours.Crystallization terminates rear mistake and filters mother liquor, and filter cake spends deionized water to cleaning solution pH value less than 10.5, obtains NaY zeolite content 45 weight portion %, zeolitic frameworks SiO after filtration
2/ Al
2o
3the crystallization product JH of moles 5.2
06.
embodiment 7
Other preparation condition is identical with example 1, is not both natural diatomaceous earth (butt): ratio=1 of protokaolin (butt): 2.Obtain NaY zeolite content 34 weight portion %, zeolitic frameworks SiO
2/ Al
2o
3the crystallization product JH of moles 5.4
07.
embodiment 8
Other preparation condition is identical with example 1, is not both natural diatomaceous earth (butt): ratio=1 of protokaolin (butt): 3.Obtain NaY zeolite content 36 weight portion %, zeolitic frameworks SiO
2/ Al
2o
3the crystallization product JH of moles 5.2
08.
embodiment 9
Other preparation condition is identical with example 1, is not both natural diatomaceous earth (butt): ratio=1 of protokaolin (butt): 8.Obtain NaY zeolite content 35 weight portion %, zeolitic frameworks SiO
2/ Al
2o
3the crystallization product JH of moles 4.5
09.
embodiment 10
Other preparation condition is identical with example 1, is not both natural diatomaceous earth (butt): ratio=1 of protokaolin (butt): 1.5.Obtain NaY zeolite content 37 weight portion %, zeolitic frameworks SiO
2/ Al
2o
3the crystallization product JH of moles 5.4
10.
In the present invention, embodiment 11 ~ 15 is the preparation of in-situ crystallization heavy oil transformation auxiliary agent.
embodiment 11
Step 21, adds deionized water 3kg in stainless steel still, stirs the lower crystallization product JH dropping into example 1 and prepare
01600g, ammonium chloride 120, exchange 1h, filter, wash and to obtain a friendship material under PH=3.0 ~ 3.5, temperature 90 ~ 95 DEG C of conditions;
Step 22, one hands over material to add 3kg water slurry, exchanges once, give-and-take conditions: PH is 3.5 ~ 4.0, temperature 90 ~ 95 DEG C, time 1h with the mixed rare earth solution containing 19.2g chlorination mishmetal, filters, washing, refilters, and hands over material for 120 DEG C dry two;
Step 23, hands over material to be placed in stainless steel by two and opens wide vessel 550 DEG C of roasting 1h, obtain a roasting material;
Step 24, a roasting material solution for the mishmetal salt containing 12.6g chlorination mishmetal exchanges once again, and give-and-take conditions, with step 22, obtain three friendship material;
Step 25, three hand over material roasting 1h at 650 DEG C, obtain two roasting material;
Step 26, two roasting material add 3kg water slurry, and the silicate fluoride solution adding 12 weight portion % under stirring carries out the reaction of liquid phase aluminium-eliminating and silicon-replenishing, makes H
2siF
6: two roasting material=0.05, are adjusted to 3.2 with the hydrochloric acid of 1N by the pH value of slurries, are then warming up to 70 DEG C, react 30 minutes, filtration, washing, dry obtained in-situ crystallization heavy oil transformation auxiliary agent ZJ
01.Its primary chemical composition and physicochemical property are in table 2.
embodiment 12
Preparation method, with embodiment 11, when carrying out the reaction of fluosilicic acid liquid phase aluminium-eliminating and silicon-replenishing unlike two roasting material, makes H
2siF
6: two roasting material=0.10, obtained in-situ crystallization heavy oil transformation auxiliary agent ZJ
02.Its primary chemical composition and physicochemical property are in table 2.
embodiment 13
Step 21, adds deionized water 3kg in stainless steel still, stirs the lower crystallization product JH dropping into example 5 and prepare
01600g, ammonium chloride 120g, exchange 1h, filter, wash and to obtain a friendship material under PH=3.0 ~ 3.5, temperature 90 ~ 95 DEG C of conditions;
Step 22, one hands over material to add 3kg water slurry, exchanges once, give-and-take conditions: PH is 3.5 ~ 4.0, temperature 90 ~ 95 DEG C, time 1h with the mixed rare earth solution containing 15g chlorination mishmetal, filters, washing, refilters, and hands over material for 120 DEG C dry two;
Step 23, hands over material to be placed in stainless steel by two and opens wide vessel 550 DEG C of roasting 1h, obtain a roasting material;
Step 24, a roasting material solution for the mishmetal salt containing 9g chlorination mishmetal exchanges once again, and give-and-take conditions, with step 22, obtain three friendship material;
Step 25, three hand over material roasting 1h at 650 DEG C, obtain two roasting material;
Step 26, two roasting material add 3kg water slurry, and the silicate fluoride solution adding 12 weight portion % under stirring carries out the reaction of liquid phase aluminium-eliminating and silicon-replenishing, makes H
2siF
6: two roasting material=0.12, are adjusted to 3.2 with the hydrochloric acid of 1N by the pH value of slurries, are then warming up to 70 DEG C, react 30 minutes, filtration, washing, dry obtained in-situ crystallization heavy oil transformation auxiliary agent ZJ
03.Its primary chemical composition and physicochemical property are in table 2.
embodiment 14
Preparation method, with embodiment 13, when carrying out the reaction of fluosilicic acid liquid phase aluminium-eliminating and silicon-replenishing unlike two roasting material, makes H
2siF
6: two roasting material=0.18, obtained in-situ crystallization heavy oil transformation auxiliary agent ZJ
04.Its primary chemical composition and physicochemical property are in table 2.
embodiment 15
Preparation method with embodiment 11, unlike, the crystallization product JH of crystallization product before modified prepared by example 6
06, when two roasting material carry out the reaction of fluosilicic acid liquid phase aluminium-eliminating and silicon-replenishing, make H
2siF
6: two roasting material=0.08, obtained in-situ crystallization heavy oil transformation auxiliary agent ZJ
05.Its primary chemical composition and physicochemical property are in table 2.
comparative example 1
By 10 kilograms of (butt) D (v, 0.5) protokaolin of 2.5 adds water to pull an oar and disperses to make the slurries that solid content is 35 weight portion %, add the sodium metasilicate (relative to protokaolin butt gross weight) of 2 weight portion % as dispersant, spray drying forming, obtains 9 kilograms of parent microballoons.Get 3 kilograms of parent microballoons roasting 3h at 940 DEG C in Muffle furnace, to change into based on spinelle and with the height soil microballoon CMA of a small amount of mullite, 3 kilograms of parent microballoons, at 870 DEG C of roasting temperature 1h, change into partially native microballoon CMB.Successively by sodium metasilicate (SiO under stirring
2250g/l, Na
2o 88g/l) 1800ml, 14% NaOH solution 670ml, directed agents (SiO
2: Al
2o
3: Na
2o: H
2o mol ratio=15: 1: 16: 320) 87.2ml, deionized water 318ml, CMA600 gram, CMB400 gram drop in stainless steel cauldron, are warming up to 92 DEG C and thermostatic crystallization 24 hours.Crystallization terminates rear mistake and filters mother liquor, and filter cake spends deionized water to cleaning solution pH value less than 10.5, obtains NaY zeolite content 28 weight portion %, zeolitic frameworks SiO after filtration
2/ Al
2o
3the crystallization product DBJH of moles 4.2
01.
In stainless steel still, add deionized water 3kg, under stirring, drop into DBJH
01600g, ammonium chloride 120, exchange 1h, filter, wash and to obtain a friendship material under PH=3.0 ~ 3.5, temperature 90 ~ 95 DEG C of conditions; One hands over material to add 3kg water slurry, exchanges once, give-and-take conditions: PH is 3.5 ~ 4.0, temperature 90 ~ 95 DEG C, time 1h with the mixed rare earth solution containing 19.2g chlorination mishmetal, filters, washing, refilters, and hands over material for 120 DEG C dry two; Hand over material to be placed in stainless steel by two and open wide vessel 550 DEG C of roasting 1h, obtain a roasting material; The one roasting material solution of the mishmetal salt containing 12.6g chlorination mishmetal exchanges once again, and give-and-take conditions, with step 22, obtain three friendship material; Three hand over material roasting 1h at 650 DEG C, obtain two roasting material; Two roasting material exchange with 120g ammonium sulfate again, filtration, washing, dry obtained contrast in-situ crystallization heavy oil transformation auxiliary agent DBZJ
01.Its primary chemical composition and physicochemical property are in table 2.
comparative example 2
Successively sodium metasilicate 7700ml, NaOH solution 400ml described in comparative example 1, directed agents 210ml, deionized water 25ml, CMA560 gram, CMB140 gram are dropped in stainless steel cauldron under stirring, be warming up to 92 DEG C and thermostatic crystallization 28 hours.Crystallization terminates rear mistake and filters mother liquor, and filter cake spends deionized water to cleaning solution pH value less than 10.5, obtains NaY zeolite content 32 weight portion %, zeolitic frameworks SiO after filtration
2/ Al
2o
3the crystallization product DBJH of moles 4.7
02.
By the method for comparative example 1 to DBJH
02carry out modification, wherein exchange with the mixed rare earth solution containing 15g chlorination mishmetal during two friendships; Exchange with the solution of the mishmetal salt containing 9g chlorination mishmetal during three friendships, obtained contrast in-situ crystallization heavy oil transformation auxiliary agent DBZJ
02.Its primary chemical composition and physicochemical property are in table 2.
embodiment 16 ~ 20
The following examples, for fixed fluidized-bed reactor, illustrate the reaction effect of FCC heavy oil transformation auxiliary agent provided by the invention.
Respectively by 30 grams of ZJ
01~ ZJ
05800 DEG C, carry out the burin-in process of 12 hours under 100% steam atmosphere condition.By the ZJ through burin-in process
01~ ZJ
05mix with industrial FCC equilibrium catalyst (the industrial trade mark is the FCC equilibrium catalyst of LBO-12, and main character is in the table 3) ratio in 10: 90.Loaded by 100g catalyst mixture in the reactor of small fixed flowing bed-tion reacting device, shown in his-and-hers watches 4, feedstock oil carries out catalytic cracking.Table 5 gives used catalyst mixture composition, reaction condition and reaction result.
comparative example 3 ~ 5
These comparative examples, for fixed fluidized-bed reactor, illustrate the reaction effect using contrast auxiliary agent.
By the method in embodiment 16, catalytic cracking is carried out to same feedstock oil, be respectively 100% industrial FCC equilibrium catalyst and DBJH unlike used catalyst
01and DBJH
02with the mixture of industrial FCC equilibrium catalyst.Composition, reaction condition and the reaction result of table 5 catalyst mixture containing contrast auxiliary agent used.
Table 1: the primary chemical composition of powdery natural diatomaceous earth
| Project | Natural diatomaceous earth | Kaolin |
| SiO 2 | 88.1％ | 48.9％ |
| Al 2O 3 | 3.2％ | 42.5％ |
| Fe 2O 3 | 1.3％ | 0.3％ |
| TiO 2 | 0.2％ | 0.9％ |
| Na 2O | 0.4％ | 0.1％ |
| K 2O | 0.4％ | 0.4％ |
| Other | 6.4％ | 6.9％ |
Table 2: the primary chemical composition of contrast in-situ crystallization heavy oil transformation auxiliary agent and physicochemical property
Note: micro-activity condition 800,17 hours, 100% steam treatment
Table 3: the industrial trade mark is the main character of the FCC equilibrium catalyst of LBO-12
| Project | Industry equilibrium catalyst LBO-12 |
| Tenor, ppm | |
| Ni | 3687 |
| V | 3356 |
| Fe | 4561 |
| Sb | 1870 |
| Ca | 1533 |
| Micro-index alive | 61 |
Table 4: feedstock oil carries out Catalytic Cracking Performance parameter
| Feedstock oil title | PetroChina Company Limited.'s North China Effect of Catalysis In Petrochemistry mixed material |
| Density (20 DEG C), gram per centimeter 3 | 0.9035 |
| Viscosity (100 DEG C), millimeter 2/ second | 10.86 |
| Freezing point, DEG C | 39 |
| Carbon residue, % by weight | 3.2 |
| Element forms, and % by weight | |
| C/H | 86.68/12.79 |
| S/N | 0.35/0.18 |
| Four composition, % by weight | |
| Saturated hydrocarbons | 58.5 |
| Aromatic hydrocarbons | 21.9 |
| Colloid | 19.1 |
| Asphalitine | 0.5 |
| Tenor, ppm | |
| V/Ni | 0.4/1.0 |
| Fe/Cu | 4.6/0.01 |
| Na | 0.6 |
| Boiling range, DEG C | |
| Initial boiling point/5% | 240/308 |
| 10％/20％ | 342/386 |
| 30％/40％ | 415/436 |
| 50％/60％ | 451/466 |
| 70％/80％ | 491/536 |
Table 5: the composition of catalyst mixture of contrast auxiliary agent and reaction condition and reaction result
Claims (6)
1. a high framework si-al ratio in-situ crystallization FCC heavy oil transformation auxiliary agent, is characterized in that: heavy oil transformation auxiliary agent by 100 weight portions in respect of NaY zeolite content 30 ~ 45 weight portion %, RE
2o
3content is 0 ~ 6.0 weight portion %, Na
2the zeolitic frameworks SiO of O0 ~ 0.35 weight portion % and surplus
2/ Al
2o
3moles 7 ~ 15.
2. prepare the method for high framework si-al ratio in-situ crystallization FCC heavy oil transformation auxiliary agent as claimed in claim 1, it is characterized in that there is the following step:
Step one: prepared by crystallization product
Step 11, protokaolin and natural diatomaceous earth are dropped in water in proportion, the slurries of solid content 30 ~ 50 weight portion % are made in making beating dispersion, dispersant is added in slurries, spray drying forming is the parent microballoon of 20 ~ 110 microns, wherein more than 90% is 40 ~ 100 microns, described spray drying tower inlet temperature 550 ~ 700 DEG C, outlet temperature 150 ~ 300 DEG C; Described dispersant comprises sodium metasilicate, NaOH, sodium pyrophosphate, calgon, and its addition is 2.0 ~ 4.0 weight portion % of natural diatomaceous earth and kaolin total amount.
Natural diatomaceous earth described in a step 11 and kaolinic weight ratio are 1: 1 ~ 1: 20.
Described natural diatomaceous earth is particle diameter≤2.0 micron after ball mill ball milling, its SiO
2>=80 weight portion %, Fe
2o
3≤ 1.5 weight portion %, K
2o+Na
2o≤1.0 weight portion %;
Described kaolin comprises soft kaolin, hard Raolinite, gangue, wherein particle diameter 2.5 ~ 3.5 microns, crystal kaolinite content>=80 weight portion %, quartz≤1.0 weight portion %, Fe
2o
3≤ 1.7 weight portion %, K
2o+Na
2o≤0.5 weight portion %.
Step 12, part parent microballoon, at 940 ~ 1000 DEG C of roasting temperature 1 ~ 3h, to change into based on spinelle and with the height soil microballoon GM of a small amount of mullite, another part, at 650 ~ 900 DEG C of roasting temperature 1 ~ 3h, changes into partially native microballoon PM;
Containing mullite 3.0 ~ 15 weight portion % in GM microballoon described in step 12, its abrasion index is less than 4%/h; Described PM microballoon is not containing mullite, and its abrasion index is less than 4%/h.
Step 13, sodium metasilicate, deionized water, NaOH, directed agents, GM, PM are added in crystallization still in proportion successively, in 90 ~ 98 DEG C of hydrothermal crystallizings 16 ~ 32 hours under stirring, cross and filter mother liquor, filter cake spends deionized water to cleaning solution pH value less than 10.5, obtains NaY zeolite content 30 ~ 65 weight portion %, zeolitic frameworks SiO after filtration
2/ Al
2o
3the crystallization product JH of moles 4.5 ~ 5.5; Stirring condition is 150 revs/min ~ 600 revs/min;
Described directed agents constitutive molar ratio is (14 ~ 16) SiO
2: (0.7 ~ 1.3) Al
2o
3: (14 ~ 16) Na
2o: (300 ~ 330) H
2o.
The weight ratio of the sodium metasilicate described in step 13, deionized water, NaOH, directed agents, GM, PM: GM/PM=10: 0 ~ 4: 6; Liquid phase SiO
2/ (GM+PM)=0.4 ~ 2.0.
The mass percent concentration of described NaOH is 14 ~ 18%.
Step 2: prepared by FCC heavy oil transformation auxiliary agent
Step 21, crystallization product JH inorganic ammonium salt solution step one obtained exchanges, inorganic ammonium salt/JH weight ratio 0.2 ~ 0.5, give-and-take conditions: PH 3.0 ~ 3.5, temperature 90 ~ 95 DEG C, time 0.5 ~ 1h, through filtering, washing and to obtain a friendship material after exchange;
Step 22, one hands over material to use the solution containing rare-earth salts to carry out ion-exchange, give-and-take conditions: PH 3.5 ~ 4.0, temperature 90 ~ 95 DEG C, time 0.5 ~ 1h, through filtration, washing after exchange, refilters, and 120 DEG C are dry that two friendships are expected;
Step 23, two hand over material roasting 1 ~ 2h at 550 ~ 600 DEG C, obtain a roasting material;
Step 24, the solution of a roasting material containing rare-earth salts carries out ion-exchange, give-and-take conditions again: PH 3.5 ~ 4.0, temperature 90 ~ 95 DEG C, time 0.5 ~ 1h, through filtration, washing after exchange, refilter, obtain three friendship material;
Step 25, three hand over material roasting 1 ~ 2h at 550 ~ 650 DEG C, obtain two roasting material;
Step 26, two roasting material are carried out the reaction of liquid phase aluminium-eliminating and silicon-replenishing with the solution of fluorine-containing silicic acid, and the addition of described fluosilicic acid is 1 ~ 30% of two roasting material weight, is preferably 5 ~ 20% of two roasting material weight.Then filter, wash, be drying to obtain required heavy oil transformation auxiliary agent, its Re
2o
3content is 0.5 ~ 8.0 weight portion %, NaY zeolite content 30 ~ 65 weight portion %, zeolitic frameworks SiO
2/ Al
2o
3moles 5.6 ~ 20, Na
2o≤0.4 weight portion %.
Said silicate fluoride solution joins in the slurries of zeolite within the time of 5 ~ 30 minutes in step 26, then reacts more than 0.5 hour at 50 ~ 90 DEG C.
3. the method for preparation according to claim 2 high framework si-al ratio in-situ crystallization FCC heavy oil transformation auxiliary agent, is characterized in that: natural diatomaceous earth described in a step 11 and kaolinic weight ratio are 1: 3 ~ 1: 15.
4. the method for preparation according to claim 2 high framework si-al ratio in-situ crystallization FCC heavy oil transformation auxiliary agent, is characterized in that: in step 21, said inorganic ammonium salt is selected from one or more combinations in interior inorganic ammonium salt of ammonium chloride, ammonium sulfate, ammonium nitrate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), ammonium phosphate, ammonium phosphite, dihydrogen phosphite ammonium, ammonium acetate, ammonium formate.
5. the method for preparation according to claim 2 high framework si-al ratio in-situ crystallization FCC heavy oil transformation auxiliary agent, it is characterized in that: in step 22, step 24, said rare-earth salts refers to the rare-earth salts for zeolite rare earth exchanged well known to those skilled in the art, is generally be key component with lanthanum and/or cerium chloride, nitrate or sulfate; Wherein the content (with oxide basis) of lanthanum and/or cerium is greater than 50 weight portion %, is preferably greater than 60 weight portion %, more preferably greater than 70 weight portion %.
6. the method for preparation according to claim 2 high framework si-al ratio in-situ crystallization FCC heavy oil transformation auxiliary agent, it is characterized in that: said silicate fluoride solution joins in the slurries of zeolite within the time of 10 ~ 20 minutes in step 26, then react 0.5 ~ 2 hour at 50 ~ 90 DEG C.
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|---|---|---|---|---|
| WO2018201046A1 (en) * | 2017-04-28 | 2018-11-01 | Basf Corporation | High activity, high gasoline yield and low coke fluid catalytic cracking catalyst |
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| CN101745418A (en) * | 2008-11-28 | 2010-06-23 | 中国石油化工股份有限公司 | Catalytic cracking catalyst, preparation and application thereof |
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| WO2013086766A1 (en) * | 2011-12-15 | 2013-06-20 | 中国石油天然气股份有限公司 | High light received heavy oil catalytic cracking catalyst and preparation method therefor |
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