CN105772074B - A kind of preparation method of catalyst for heavy oil catalytic cracking - Google Patents
A kind of preparation method of catalyst for heavy oil catalytic cracking Download PDFInfo
- Publication number
- CN105772074B CN105772074B CN201410827885.2A CN201410827885A CN105772074B CN 105772074 B CN105772074 B CN 105772074B CN 201410827885 A CN201410827885 A CN 201410827885A CN 105772074 B CN105772074 B CN 105772074B
- Authority
- CN
- China
- Prior art keywords
- added
- catalyst
- preparation
- catalytic cracking
- oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
A kind of preparation method of catalyst for heavy oil catalytic cracking.The preparation method includes：Reaction kettle first is added in boehmite, clay, Aluminum sol and inorganic acid and is uniformly mixed, form matrix slurries, acid adding amount is that the pH value of matrix slurries is made to be adjusted to 0.5~2.0, stir 0.5~2h, then alkaline medium is added into matrix slurries and pH value is adjusted to 3.5~5.5,1~12h is cured, molecular sieve homogeneous is added and forms catalytic cracking catalyst slurry, gained catalytic cracking catalyst slurry is spray-dried up to catalyst.Preparation method disclosed in this invention can improve the pore volume of catalyst under the premise of ensureing catalyst wear strength, improve the heavy oil pyrolysis ability of catalyst.
Description
Technical field
The present invention relates to the preparation methods of oil refining catalyst, are more particularly to the preparation side of catalyst for heavy oil catalytic cracking
Method.
Background technology
Semi-synthetic catalytic cracking catalyst is mainly made of molecules of active components sieve and matrix, and matrix includes carrier (such as height
Ridge soil) and binder (such as Aluminum sol, Ludox) two parts, main material of the matrix as catalytic cracking catalyst account for catalysis
50% or more of agent ingredient.In the semi-synthetic catalyst of early stage, matrix is only used as carrier, predominantly catalyst provide compared with
The physical properties such as good wear resistance, moderate bulk density.Since the 1990s, the heaviness of world's crude oil and
In poor quality is on the rise, and in order to make heavy oil molecules close to catalyst active center, realizes the order cracking of heavy oil macromolecular, matrix
In catalyst for heavy oil catalytic cracking in addition to undertaking general carrier function, certain pore structure and activated centre, base are also provided
The suitable pore size distribution of matter and acid centre are conducive to the diffusion of heavy oil macromolecular and precracked, improve the residual oil cracking of molecular sieve
Ability, meanwhile, aperture increases are conducive to improve the diffusion rate of macromolecular hydrocarbon, and overcracking is inhibited to generate coke.
Patent CN1098130A discloses a kind of preparation method of catalytic cracking catalyst：First clay and deionized water are mixed
Mashing is closed, hydrochloric acid acidification is added, is then added boehmite, then by gained slurries in 50~80 DEG C of agings 0.5~2 hour,
Then Aluminum sol and molecular sieve pulp is added, be uniformly mixed and is spray-dried.
Patent CN1690168A discloses the preparation method of the hydrocarbon cracking catalyzer containing molecular sieve, including by Aluminum sol, water
It closes aluminium oxide, clay, acid, molecular sieve and water mashing to be uniformly mixed, a kind of slurries is made, the slurries being then dried to obtain.It is described
Hydrated alumina contains a kind of modified hydrated alumina, and the modified hydrated alumina is to roast at least 10 points through 150~400 DEG C
The hydrated alumina of clock, in mashing, the acid is added after Aluminum sol and hydrated alumina.
A kind of preparation method of Cracking catalyst includes in patent CN1246515A：By molecular sieve pulp, Aluminum sol, quasi- thin
Diaspore, clay and inorganic acid mashing are uniformly mixed and catalyst slurry are made, and are then spray-dried；It is characterized in that molecular sieve
It is added before clay and inorganic acid, inorganic acid is added after Aluminum sol, and preferably inorganic acid in Aluminum sol and intends thin water
It is added after aluminium stone, the addition sequence of rest materials is not particularly limited.
A kind of preparation method of Cracking catalyst is disclosed in patent CN1247885A, this method includes by molecule screening the pulp
Liquid, Aluminum sol, boehmite, clay and inorganic acid are beaten, and it is 25~45% to make the solid content of slurries, and feature exists
It is added before clay and inorganic acid in Aluminum sol, molecular sieve pulp is added after inorganic acid, and preferably inorganic acid is in aluminium
It is added after colloidal sol and boehmite, though the patent can improve the quasi- thin water of the solid content of catalyst, Aluminum sol and acidification
Aluminium ion mainly exists with oligomer in aluminium stone, will unavoidably block the duct of clay, causes matrix pore volume smaller, most
The pore structure and heavy oil conversion performance of catalyst are influenced eventually.
Disclosed in patent CN1270203A it is a kind of improve catalyst spray slurry solid content method, i.e., molecular sieve and/
Or Aluminum sol is added before clay and inorganic acid, inorganic acid is added after Aluminum sol, and preferably inorganic acid is in Aluminum sol
It is added with after boehmite, the addition sequence of rest materials is not particularly limited, and one kind is added in spray slurry
Dispersant, this dispersant are one kind or their mixtures in ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, can be significantly
The solid content of spray slurry is improved, gelation time is shortened.
The preparation method for the Cracking catalyst that patent CN1311288A is provided includes：By molecular sieve pulp, Aluminum sol, quasi- thin
Diaspore, clay and inorganic acid mashing are uniformly mixed and catalyst slurry are made, and are then spray-dried；It is characterized in that molecular sieve
Slurries and/or Aluminum sol are added before clay and inorganic acid, and inorganic acid is added after Aluminum sol, and preferably inorganic acid exists
It is added after Aluminum sol and boehmite, the addition sequence of rest materials is not particularly limited, and before spray drying
Described catalyst slurry in a kind of alkali silicate is added.
Patent US7727924, US20080058197 and CN101134905A provide a kind of preparation of catalytic cracking catalyst
Method, this method include：By clay, molecular sieve pulp, containing al binder, boehmite and inorganic acid be uniformly mixed be made
Then catalyst slurry is spray-dried, it is characterised in that inorganic acid is added before boehmite, molecular sieve inorganic acid it
After be added, and in FCC catalyst preparation process, a kind of phosphorous dispersant is added, significantly reduces the viscous of catalyst slurry
Degree, improves the mobility of catalyst slurry.
The preparation method for the cracking catalyst for petroleum hydrocarbon that patent CN1388213A is provided is will be after clay slurry acid processing
Boehmite is added, carries out burin-in process, water glass solution is added, after being beaten uniformly, Aluminum sol is added, adds dispersion
Uniform molecular sieve pulp is spray-dried, washing.
The preparation method of patent CN102049311A catalytic cracking of petroleum hydrocarbon catalyst provided by the invention, by quasi- thin water aluminium
After stone mashing, water glass solution is added, is then added mineral acid acidified, adds that Aluminum sol, kaolin, molecular sieve etc. are other to urge
Agent component, spray drying after being beaten uniformly, washing.
Patent CN1240813A discloses a kind of preparation method of Cracking catalyst：Clay is mixed with water, mashing dispersion adds
Enter hydrochloric acid and boehmite stirs 30 minutes, carries out acidification peptization for the first time, molecular sieve pulp is then added, stir 20 points
Aluminum sol and hydrochloric acid is added in clock, carries out second of acidification peptization, is spray-dried, washing.
Above-mentioned patent is all that unmodified Aluminum sol or acidification pseudo-boehmite are directly mixed into matrix slurries with clay, no
Be that Aluminum sol, clay, molecular sieve pulp, boehmite, the charging sequence of acid are different or different dispersant is added carries
Si modification catalyst is added in the solid content of high catalyst.It prepares in catalyst process and exists according to prior art or modified technique
Outstanding problem be：Unmodified Aluminum sol or acidification pseudo-boehmite are added directly into matrix slurries or catalyst slurry, by
In aluminium ion mainly with Al13Form exists, and Al13Aggregate particle size is smaller (1nm), is easy to block in matrix or catalyst
Hole causes catalyst mesoporous pore volume small, and heavy oil cracking ability is poor.Alkali carries height slurry is added in patent CN101624536A in slurries
Then the pH value of liquid is added acid, reduces the pH value of slurries, can improve the stability of catalyst preparation, but pore volume increase has
Limit, and it is cumbersome.
Invention content
The purpose of the present invention is to provide a kind of preparation method of catalyst for heavy oil catalytic cracking, this method is ensureing to be catalyzed
Under the premise of agent wear strength, the pore volume of catalyst can be improved, improve the heavy oil pyrolysis ability of catalyst.
A kind of preparation method of catalyst for heavy oil catalytic cracking provided by the present invention, including：First by boehmite, viscous
Soil, Aluminum sol and inorganic acid are added reaction kettle and are uniformly mixed, and form matrix slurries, inorganic acid addition is to make matrix slurries
PH value is adjusted to 0.5~2.0, stirs 0.5~2h, and alkaline medium is then added into matrix slurries is adjusted to 3.5~5.5 by pH value,
1~12h is cured, molecular sieve homogeneous is added and forms catalytic cracking catalyst slurry, gained catalytic cracking catalyst slurry is sprayed
Mist is drying to obtain catalyst.
A kind of preparation method of catalyst for heavy oil catalytic cracking provided by the present invention, by water, boehmite, clay,
Aluminum sol and inorganic acid are added reaction kettle and are uniformly mixed, and during forming matrix slurries, the addition sequence of various materials does not have
It is restricted：Clay, Aluminum sol, boehmite and water can be added simultaneously, be stirring evenly and then adding into inorganic acid；It can also incite somebody to action
After one or both of clay, Aluminum sol, boehmite are stirred evenly with water, remaining matrix is added, nothing is then added
Machine acid；After can also stirring evenly one or both of clay, Aluminum sol, boehmite with water, remaining base is added
Matter and inorganic acid, remaining matrix and inorganic acid addition sequence are without limitation；If after meeting all matrix additions, matrix slurry
The pH value of liquid is adjusted to 0.5~2.0, preferably 0.5~1.8.Preparation method disclosed by the invention is in the process for forming matrix slurries
In, preferably first reaction kettle is added in clay and water by the addition sequence of various materials, and inorganic acid is then added, adds Aluminum sol
And boehmite.
Alkaline medium is added in matrix slurries in a kind of preparation method of catalyst for heavy oil catalytic cracking provided by the present invention
PH value is adjusted to 3.5~5.5, cures 1~12h, which need not heat up, i.e., consistent with laboratory's environment temperature,
It namely carries out under room temperature, the temperature range is at 0~40 DEG C, usually 0~30 DEG C.
A kind of preparation method of catalyst for heavy oil catalytic cracking provided by the present invention, the catalytic cracking catalyst,
The catalyst is 100% calculating with butt quality, including 15~60% clays, molten by 3~18% aluminium of aluminum oxide gauge
Glue, 15~50% molecular sieves, by 8~30% boehmite of aluminum oxide gauge, 0~10% selected from rare earth oxide, oxidation
The one or more oxides or its predecessor of phosphorus, aluminium oxide-silicon oxide.
A kind of preparation method of catalyst for heavy oil catalytic cracking provided by the present invention, clay, Aluminum sol, molecular sieve and quasi-
The type of boehmite is technology known in the field, is gone back in the catalytic cracking catalyst described in method provided by the invention
Can contain it is opposite with catalytic cracking catalyst quality 0~10%, preferably 0.2~6% selected from rare earth oxide, phosphorous oxide, oxygen
Change the one or more oxides or its predecessor of aluminium-silica；It is preferred that it is opposite with catalytic cracking catalyst quality 0.2~
6%, more preferable 0.2~2% rare earth oxide or rare earth oxide predecessor.
A kind of preparation method of catalyst for heavy oil catalytic cracking provided by the present invention, rare earth oxide, phosphorous oxide, oxidation
The one or more oxides or its predecessor of aluminium-silica are added in preparing matrix slurry processes, preferably in inorganic acid
It is added before being added；Rare earth oxide, phosphorous oxide, one or more oxides of aluminium oxide-silicon oxide or its predecessor also may be used
To be added simultaneously or before molecular sieve addition, after molecular sieve addition in the process and molecular sieve for forming catalyst slurry.
A kind of preparation method of catalyst for heavy oil catalytic cracking provided by the present invention, the clay be selected from kaolin,
One or more of halloysite, galapectite, montmorillonite, bentonite, or modified clay, wherein modified clay is through 500
One or more of DEG C~900 DEG C of the roasting kaolin of 0.5~3h, halloysite, galapectite, montmorillonite, bentonites.
A kind of preparation method of catalyst for heavy oil catalytic cracking provided by the present invention, the molecular sieve are y-type zeolite,
Including various modified zeolite of Y-type or one of y-type zeolite and ZSM zeolite, β zeolites, omega zeolite, MCM zeolites, SAPO zeolites
Or several mixture；The mixture of wherein preferred y-type zeolite or y-type zeolite and ZSM-5 zeolite.Wherein described modification Y
Type zeolite is HY, NH4Y, one kind or their mixture of REY, USY, REUSY, other element modified Y zeolites.
A kind of preparation method of catalyst for heavy oil catalytic cracking provided by the present invention, the boehmite can be
Boehmite, three boehmites, bayerite, preferably boehmite.
A kind of preparation method of catalyst for heavy oil catalytic cracking provided by the present invention, the inorganic acid be selected from hydrochloric acid,
The one or more of nitric acid, phosphoric acid, sulfuric acid, preferably hydrochloric acid and/or nitric acid.
A kind of preparation method of catalyst for heavy oil catalytic cracking provided by the present invention, the alkaline medium are selected from carbonic acid
The one or more of ammonium, ammonium hydrogen carbonate, aluminium hydroxide, ammonium hydroxide, sodium metaaluminate, alkaline silica sol, waterglass.
A kind of preparation method of catalyst for heavy oil catalytic cracking provided by the present invention, acid adding adjust matrix slurry pH value mistake
Cheng Zhong adjusts pH value in 0.5~2.0, preferably 0.5~1.8, stirs 0.5~2h.
A kind of preparation method of catalyst for heavy oil catalytic cracking provided by the present invention, alkaline medium adjust matrix slurries pH
During value, pH value is adjusted 3.5~5.5, cures 1~12h, pH value is preferably 4.0~5.2, and the curing time is preferably 1~
5h。
A kind of preparation method of catalyst for heavy oil catalytic cracking provided by the present invention, preferably acid adding adjust matrix slurries pH
Value 0.5~1.8 stirs 0.5~2h；It is 4.0~5.2 that alkaline medium, which adjusts matrix slurry pH value, the curing time is preferably 1~
5h。
For using Aluminum sol for the catalytic cracking catalyst of binder, aluminum ions coherent condition is to influence catalyst pores
An important factor for structure and catalyst wear strength.Therefore, how to control aluminum ions coherent condition becomes improvement catalyst
The key point of intensity and pore volume.The key problem in technology of the present invention is to keep the lower of matrix slurries first in matrix slurries
PH value can both ensure the complete peptization of boehmite, improve the adhesive property of boehmite, ensure catalyst strength,
The activated aluminum that clay can fully be extracted again increases the pore volume of clay, while lower pH value can also be modified clay, improves
The acidity of matrix argillaceous is wrapped, activated centre quantity is increased, improves heavy oil conversion performance；Then alkali carries Super matrix slurries are added
PH value, change aluminum ions coherent condition, aluminium ion avoided to block matrix duct and molecular sieve pore passage, be catalyzed after improving molding
The pore volume of agent；And post curing, increase aluminum ions aggregation grain size, reduces aluminium ion and block molecular sieve pore passage；Molecular sieve pulp
The structure that can avoid that molecular sieve is destroyed because the pH value of slurries is too low is added after matrix adjusts pH value.Simultaneously as the present invention
Preparation method, matrix slurries first keep lower pH value, and alkali carries high ph-values are then added and carry out aging, ageing process need not rise
Temperature.Generally speaking, compared with the method for the prior art, the catalyst of preparation has preferably preparation method disclosed in this invention
Wear strength can improve the pore volume of catalyst, improve the heavy oil pyrolysis ability of catalyst；Substantially reduce catalyst simultaneously
The energy consumption and production cost of manufacturing enterprise.
Compared with existing method for preparing catalyst, method for preparing catalyst provided by the invention has larger pore volume, and
Catalyst strength is high；Not only it can guarantee the reactivity worth of catalyst, but also the service life of catalyst can be extended, to improving enterprise of refinery
Benefit and cost-effective have great importance；This method preparation process is simple, and raw material cost is low, can be on existing apparatus
Realize catalyst production, investment in productive enterprise is low, and income is good.
Specific implementation mode
In order to which the present invention is further detailed, spy enumerates following embodiment, but the present invention is not limited in implementing
Example.
(1) analysis test method：
| Project | Method | Standard No. |
| Pore volume mL.g-1 | Water droplet method | Q/SYLS 0521-2002 |
| Abrasion index m% | Gas lift method | Q/SYLS 05182002 |
| Micro-activity (4 hours) m% | Miniature fixed bed reaction | Q/SYLS 05892002 |
| Reaction selectivity | Fixed fluidized bed reaction | Q/SYLS 0641-2002 |
| Octane number | Chromatography | M213.0207-2003 |
| Gasoline forms v% | Chromatography | Beijing Shi Keyuan softwares |
(2) places of origin of raw materials used in and specification
Kaolin：China Kaolin Co., Ltd, 86 heavy % of kaolinite.
Bentonite：Shandong Weifang prosperity bentonite factory, 80 heavy % of montmorillonite.
Montmorillonite：Moisten Longhua work Co., Ltd, 98 heavy % of montmorillonite in the Inner Mongol.
Galapectite：Four positive mining industry Co., Ltd of Nanning, 95 heavy % of kaolinite.
Aluminum sol：Catalyst Factory of Lanzhou Petrochemical Company, Al20324.56 heavy % of content, Al/CI molar ratios are 1.24.
Polymeric aluminum chloride：Zhejiang Hangzhou Xi Feng trade Co., Ltds, Al20329 heavy % of content.
REUSY zeolites, USY zeolite, REY zeolites, ZSM-5 are Catalyst Factory of Lanzhou Petrochemical Company production.
Boehmite：Alumina content is 75.4 heavy %, the production of Shandong Alumina factory.
Hydrochloric acid, nitric acid, rare earth chloride, ammonium hydroxide：Industrial goods come from Catalyst Factory of Lanzhou Petrochemical Company.
Alkaline silica sol：Dalian Inst of Chemicophysics, Chinese Academy of Sciences produces, Si0227.0 heavy % of content, with hydrochloric acid tune
It is 10.5 to save pH value.
Waterglass：Si0231.0 heavy % of content, modulus (m) 3.25, the production of Baoding Run Feng Industrial Co., Ltd.s.
Sodium metaaluminate：Al2O355 heavy % of content, the production of Zibo Lear Chemical Co., Ltd..
Embodiment 1
1140 grams of deionized waters of addition, 2078 grams of kaolin, 1656 grams of boehmites, 2174 grams of aluminium are molten in a kettle
230 grams a concentration of 35% of hydrochloric acid, pH value 0.7 is added in glue, mashing after ten minutes, and 116 grams of ammonium hydroxide are added after 1 hour in stirring,
PH value is 4.8 after mixing, is cured 12 hours, and stirring adds oneself and is less than to average grain diameter with colloid mill is levigate after 30 minutes
5 microns of the mixed serum being made of 2060 grams of REUSY molecular sieves, 123 grams of ZSM-5 and 2388 gram of deionized waters, is beaten 30 points
It is spray-dried after clock, gained catalyst microspheres is roasted 0.5 hour at 500 DEG C, 8 times of deionized waters, stirring is then added
Uniformly, it is washed 15 minutes at 80 DEG C, the FCC catalyst that filtration drying is prepared up to the method for the present invention is denoted as A1.
The abrasion index of catalyst A1 is 1.7, pore volume 0.40mL.g-1, micro-activity 81.
Embodiment 2
2262 grams of deionized waters, 1656 grams of boehmites, 2174 grams of Aluminum sols, 1078 Ke Mengtuo are added in a kettle
Soil, 968 grams of modified montmorillonoids (montmorillonite of 650 DEG C of roastings 2 hours), mashing is added 200 grams a concentration of 35% after ten minutes
98 grams of alkaline silica sols are added after 30 minutes in hydrochloric acid, pH value 1.3, stirring, and pH value is 5.0 after mixing, is cured 2 hours,
Stirring added after 30 minutes own colloid mill it is levigate to average grain diameter less than 5 microns of 1937 grams of REUSY molecular sieves, 123 grams
The molecular sieve pulp that ZSM-5 molecular sieve is mixed with 3510 grams of deionized waters, mashing are spray-dried after 30 minutes, gained are urged
Agent microballoon roasts 0.5 hour at 500 DEG C, and 8 times of deionized waters are then added, stirs evenly, is washed 15 minutes at 80 DEG C, filters
It is drying to obtain the FCC catalyst of the method for the present invention preparation, is denoted as A2.
The abrasion index of catalyst A2 is 1.5, pore volume 0.42mL.g-1, micro-activity 79.
Comparative example 1
This comparative example is the effect that method with reference to described in Chinese patent CN1247885A prepares FCC catalyst.
2174 grams of Aluminum sols and 2140 grams of deionized waters are added in a kettle, are added while agitating 1656 grams quasi- thin
2078 grams of kaolin are added in diaspore, mashing after twenty minutes, and 355 grams a concentration of 35% of hydrochloric acid is added after being stirred for 45 minutes,
The levigate 2060 grams of REUSY molecular sieves for being less than 5 microns to average grain diameter of the own colloid mill of addition after being beaten again 30 minutes, 123 grams
The molecular sieve pulp that ZSM-5 is mixed with 2388 grams of deionized waters, mashing is spray-dried after 30 minutes, and gained catalyst is micro-
Ball roasts 0.5 hour FCC catalyst prepared to get the method for the present invention at 500 DEG C, is denoted as B1.
The abrasion index of catalyst B1 is 1.9, pore volume 0.35mL.g-1, micro-activity 73.
Comparative example 2
This comparative example is the effect that method with reference to described in Chinese patent CN1311288A prepares FCC catalyst.
Addition is milled to average grain diameter less than 5 microns by 4850 deionized waters, 123 grams of ZSM- with colloid mill in a kettle
The slurries of 5 and 2060 grams of REUSY molecular sieves composition are being added 2174 grams of Aluminum sols, 2078 grams are then added while agitating
1656 grams of boehmites are added after 15 minutes in kaolin, stirring, stir the 20 minutes hydrochloric acid for being added 230 grams a concentration of 35%,
Mashing is spray-dried after 30 minutes, when gained catalyst microspheres roast at 500 DEG C to 0.5, then 8 times of deionizations of addition
Water stirs evenly, and is washed 15 minutes at 80 DEG C, the FCC catalyst that filtration drying is prepared up to the method for the present invention is denoted as B2.
The abrasion index of catalyst B2 is 1.7, pore volume 0.34mL.g-1, micro-activity 73.
Comparative example 3
This comparative example is to use 1 raw materials used composition of embodiment, the side with reference to described in Chinese patent CN101624536A
Method prepares the effect of FCC catalyst.
2262 grams of deionized waters, 1656 grams of boehmites are added in a kettle, mashing is added a concentration of after ten minutes
Slurry pH value is adjusted to 3.5 by 35% hydrochloric acid, then is beaten 20 minutes, and ammonium hydroxide, which is then added, makes its pH value be 8.2, is beaten 20 points
Clock.Slurry pH value is adjusted to 3.5 with hydrochloric acid again, is beaten 20 minutes, 2078 grams of kaolin are added, is beaten 15 minutes, is added 2388
Gram deionized water, be then added own colloid mill it is levigate to average grain diameter be less than 5 microns by 2060 grams of REUSY molecular sieves with
123 grams of ZSM-5 are stirred 15 minutes, and then at 2174 grams of Aluminum sols are added with stirring, mashing is spray-dried after 30 minutes, will
Gained catalyst microspheres roast 0.5 hour at 500 DEG C, and 8 times of deionized waters are then added, stir evenly, and 15 points are washed at 80 DEG C
Clock, the FCC catalyst that filtration drying is prepared up to the method for the present invention, is denoted as B3.
The abrasion index of catalyst B3 is 1.9, pore volume 0.30mL.g-1, micro-activity 77.
Comparative example 4
Method with reference to described in Chinese patent CN103031062A prepares FCC catalyst.
At 15 DEG C, by 1140 grams of deionized waters, 1656 grams of boehmites, a concentration of 35% hydrochloric acid is in the first plastic
It is mixed in kettle, mashing 20min obtains the first slurries, wherein the dosage of hydrochloric acid so that the PH of the first slurries is 2.5；By the first slurry
Liquid is fully incorporated in the second colloid generating kettle, is warming up to 70 DEG C, and ammonium hydroxide is added into the first slurries under stiring, is stirred after adding
20min obtains the second slurries, and the dosage of wherein ammonium hydroxide so that the PH of the second slurries is 6.5；By 2078 grams of kaolin, 1020 grams are gone
Ionized water is added in the second above-mentioned slurries, is beaten 15 minutes, and it is levigate micro- less than 5 to average grain diameter that own colloid mill is then added
The mixed serum of rice being made of 2060 grams of REUSY molecular sieves, 123 grams of ZSM-5 and 2388 gram of deionized waters, is stirred 15 minutes,
2174 grams of Aluminum sols are added thereto again, mashing is spray-dried after 30 minutes, gained catalyst microspheres are roasted at 500 DEG C
0.5 hour, 8 times of deionized waters are then added, stirs evenly, is washed 15 minutes at 80 DEG C, filtration drying is up to the method for the present invention
The FCC catalyst of preparation, is denoted as B4.
The abrasion index of catalyst B4 is 1.9, pore volume 0.34mL.g-1, micro-activity 77.
Embodiment 3
700 grams of deionized waters, 2174 grams of Aluminum sols, 1280 grams of kaolin and 550 grams of galapectites are added in a kettle, beat
200 grams a concentration of 25% of hydrochloric acid is added in slurry after ten minutes, and 1904 grams are added under stirring after mixing intends thin water aluminium
Stone, pH value is 1.2 after homogeneous, and 98 grams of sodium metaaluminates are added after 2 hours in stirring, and pH value is 4.3 after mixing, and curing 10 is small
When, the levigate 1860 grams of REUSY molecular sieves for being less than 5 microns to average grain diameter of the own colloid mill of addition after stirring 30 minutes, 100 grams
The molecular sieve pulp that ZSM-5 is mixed with 2905 grams of deionized waters, mashing is spray-dried after 30 minutes, and gained catalyst is micro-
Ball roasts 0.5 hour at 500 DEG C, and 8 times of deionized waters are then added, stirs evenly, is washed 15 minutes at 80 DEG C, filtration drying is
FCC catalyst prepared by the method for the present invention is obtained, A3 is denoted as.
The abrasion index of catalyst A3 is 1.5, pore volume 0.42mL.g-1, micro-activity 78.
Embodiment 4
2040 grams of deionized waters, 3170 grams of Aluminum sols and 4098 grams of kaolin are added in a kettle, mashing is after ten minutes
230 grams a concentration of 35% of nitric acid is added, 2656 grams of boehmites are added under stirring after mixing, stirs 30 points
A concentration of 22% re chloride is added after clock (with RE2O3Meter) 145 grams, pH value is 0.5 after stirring 30 minutes, then plus
Enter 69 grams of aluminium hydroxides, pH value is 3.6 after mixing, is cured 3 hours, and it is levigate extremely that own colloid mill is added after 30 minutes in stirring
Average grain diameter being mixed by 1570 grams of REUSY molecular sieves, 398 grams of REY, 102 grams of β zeolites and 3510 grams of deionized waters less than 5 microns
The molecular sieve pulp of conjunction, mashing are spray-dried after 30 minutes, gained catalyst microspheres are roasted 1 hour at 400 DEG C, then
8 times of deionized waters are added, stirs evenly, is washed 15 minutes at 80 DEG C, the FCC catalysis that filtration drying is prepared up to the method for the present invention
Agent is denoted as A4.
The abrasion index of catalyst A4 is 1.6, pore volume 0.40mL.g-1, micro-activity 82.
Embodiment 5
3174 grams of Aluminum sols are added in a kettle, 2150 grams of deionized waters, 5089 grams of kaolin, 2656 grams are intended thin water aluminium
180 grams a concentration of 35% of nitric acid, pH value 2.0 is added in stone mashing after ten minutes, and 78 grams of hydroxides are added after 50 minutes in stirring
Magnesium, pH value 5.2 cure 8 hours, be added after stirring being added 30 minutes own colloid mill it is levigate to average grain diameter less than 5 microns
By 984 grams of USY molecular sieves, 986 grams of REY, the molecular sieve pulp that 102 grams of ZSM-5 zeolites are mixed with 3510 grams of deionized waters is beaten
Slurry is spray-dried after 30 minutes, and gained catalyst microspheres are roasted 0.5 hour at 600 DEG C, 8 times of deionizations are then added
Water stirs evenly, and is washed 15 minutes at 80 DEG C, the FCC catalyst that filtration drying is prepared up to the method for the present invention is denoted as A5.
The abrasion index of catalyst A5 is 1.9, pore volume 0.37mL.g-1, micro-activity 79.
Embodiment 6
506 grams of deionized waters, 3201 grams of Aluminum sols and 1676 grams of kaolin are added in a kettle, mashing adds after ten minutes
Enter 150 grams a concentration of 35% of hydrochloric acid, 1240 grams of boehmites are added under stirring after mixing, stirs 20 minutes
PH value is 1.7 afterwards, and 136 grams of waterglass are added after 1 hour in stirring, and pH value is 5.3 after mixing, is cured 5 hours, stirs 25 points
The levigate 2270 grams of REUSY molecular sieves and 3510 grams of deionized waters to average grain diameter less than 5 microns of own colloid mill are added after clock
Mixed molecular sieve pulp, mashing are spray-dried after 30 minutes, gained catalyst microspheres are roasted 0.5 hour at 500 DEG C,
Then 8 times of deionized waters are added, stirs evenly, is washed 15 minutes at 80 DEG C, the FCC that filtration drying is prepared up to the method for the present invention
Catalyst is denoted as A6.
The abrasion index of catalyst A6 is 1.9, pore volume 0.35mL.g-1, micro-activity 82.
Embodiment 7
3614 grams of deionized waters, 1087 grams of Aluminum sols are added in a kettle, 4680 grams of kaolin are beaten and add after ten minutes
Enter 88 grams a concentration of 20% of hydrochloric acid, 1656 grams of boehmites are added under stirring after mixing, stirs 10 minutes
PH value is 1.9, stirs 90 minutes and 126 grams of ammonium carbonates are added, and pH value is 4.2 after mixing, and aging 7 hours is stirred 30 minutes
It is mixed that the levigate 1585 grams of REUSY molecular sieves and 4198 grams of deionized waters to average grain diameter less than 5 microns of own colloid mill are added afterwards
The molecular sieve pulp of conjunction, mashing are spray-dried after 30 minutes, gained catalyst microspheres are roasted 0.5 hour at 500 DEG C, so
8 times of deionized waters are added afterwards, stirs evenly, is washed 15 minutes at 80 DEG C, filtration drying is urged up to FCC prepared by the method for the present invention
Agent is denoted as A7.
The abrasion index of catalyst A7 is 1.3, pore volume 0.39mL.g-1, micro-activity 82.
The experimental result of comprehensive analysis Examples 1 to 7 and comparative example 1~4, it can be seen that using provided by the invention
Catalytic cracking catalyst preparation method can effectively improve catalysis under conditions of ensureing that catalyst has relatively low abrasion index
Agent pore volume and micro-activity.Table 2 is that the method for the present invention prepares catalyst and comparative catalyst on fixed fluidized bed device
Evaluation result.500 DEG C of fixed fluidized bed reaction temperature, oil ratio 4, air speed 15h-1, feedstock oil is that Xinjiang Oil Regions mix refining 30%
Decompression residuum.
Evaluation result of 2 catalyst of table on fixed fluidized bed
| Experiment numbers | Embodiment 1 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Catalyst | A1 | B1 | B2 | B3 | B4 |
| Abrasion index, % | 1.7 | 1.9 | 1.7 | 1.9 | 1.9 |
| Pore volume, mL.g-1 | 0.40 | 0.35 | 0.34 | 0.30 | 0.34 |
| Micro-activity, % | 81 | 73 | 73 | 77 | 77 |
| Dry gas, % | 1.78 | 1.81 | 1.81 | 1.80 | 1.78 |
| Liquefied gas, % | 16.17 | 16.07 | 16.05 | 15.91 | 15.86 |
| Gasoline, % | 48.64 | 48.10 | 48.06 | 48.30 | 48.19 |
| Diesel oil, % | 17.32 | 17.42 | 17.50 | 17.13 | 17.44 |
| Heavy oil, % | 7.90 | 8.38 | 8.48 | 8.58 | 8.63 |
| Coke, % | 8.03 | 8.00 | 7.88 | 8.15 | 8.08 |
| It amounts to, % | 99.84 | 99.78 | 99.88 | 99.87 | 99.79 |
| Conversion ratio, % | 74.63 | 73.98 | 73.77 | 74.16 | 74.09 |
| Total liquid yield, % | 82.14 | 81.59 | 81.61 | 81.30 | 81.49 |
| It is light to receive, % | 65.96 | 65.52 | 65.56 | 65.43 | 65.65 |
| Gasoline olefin, v% | 13.43 | 15.13 | 15.08 | 15.29 | 15.18 |
| MON | 81.6 | 81.4 | 81.3 | 81.7 | 81.5 |
| RON | 91.5 | 91.9 | 91.5 | 91.6 | 91.4 |
As known from Table 2, compared with catalyst B1 and B3 prepared by comparative example, the catalyst A1 of present invention process method preparation
With best heavy oil conversion performance and highest total liquid yield, while the olefin(e) centent for generating gasoline is relatively low, the totality of catalyst
Reactivity worth is improved.
Claims (11)
1. a kind of preparation method of catalyst for heavy oil catalytic cracking, it is characterised in that this method includes：First by water, quasi- thin water aluminium
Stone, clay, Aluminum sol and inorganic acid are added reaction kettle and are uniformly mixed, and form matrix slurries, and inorganic acid addition satisfaction makes base
The pH value of chylema liquid is 0.5~1.8, stirs 0.5~2h, and alkaline medium is then added into matrix slurries is adjusted to 3.5 by pH value
~5.5,1~12h is cured, molecular sieve homogeneous is added and forms catalytic cracking catalyst slurry, by gained catalytic cracking catalyst
Slurries are spray-dried up to catalyst for heavy oil catalytic cracking.
2. preparation method according to claim 1, it is characterised in that described is first molten by water, boehmite, clay, aluminium
Glue and inorganic acid are added reaction kettle and are simultaneously uniformly mixed, and form the processes of matrix slurries and are realized by one of following modes：Mode
1, clay, Aluminum sol, boehmite and water are added simultaneously, are stirring evenly and then adding into inorganic acid；Mode 2, clay, aluminium is molten
After one or both of glue, boehmite are stirred evenly with water, remaining matrix is added, inorganic acid is then added；Mode
3：After one or both of clay, Aluminum sol, boehmite are stirred evenly with water, remaining matrix and inorganic is added
Acid, remaining matrix and inorganic acid addition sequence are without limitation.
3. preparation method according to claim 2, it is characterised in that be in the process for forming matrix slurries：By clay and water
After stirring evenly, inorganic acid is added, adds Aluminum sol and boehmite.
4. preparation method according to claim 1 or 2, it is characterised in that the inorganic acid is selected from hydrochloric acid, nitric acid, phosphorus
The one or more of acid, sulfuric acid；The alkaline medium is selected from ammonium carbonate, ammonium hydrogen carbonate, aluminium hydroxide, ammonium hydroxide, meta-aluminic acid
The one or more of sodium, alkaline silica sol, waterglass.
5. preparation method according to claim 1 or 2, it is characterised in that alkaline medium is added in the slurries to matrix
PH value is adjusted to 4.0~5.2, cures 1~5h.
6. preparation method according to claim 1 or 2, it is characterised in that water, boehmite, clay, Aluminum sol and
Inorganic acid is added reaction kettle and is uniformly mixed, and is formed in matrix slurry processes and is added selected from rare earth oxide, phosphorous oxide, aluminium oxide-
The one or more oxides or predecessor of silica；Or it is added in the process for forming catalytic cracking catalyst slurry and is selected from oxygen
The one or more oxides or its predecessor of change rare earth, phosphorous oxide, aluminium oxide-silicon oxide.
7. preparation method according to claim 6, it is characterised in that described is selected from rare earth oxide, phosphorous oxide, aluminium oxide-
The one or more oxides or its predecessor of silica are added in preparing matrix slurry processes, and are added in inorganic acid
It is added before.
8. preparation method according to claim 1, it is characterised in that the catalyst for heavy oil catalytic cracking, with catalyst
Butt quality is 100% calculating, including 15~60% clays, by 3~18% Aluminum sol of aluminum oxide gauge, 15~50% molecules
Sieve, by 8~30% boehmite of aluminum oxide gauge.
9. preparation method according to claim 8, it is characterised in that the catalyst for heavy oil catalytic cracking, also include with
Oxidation material gauge 0~10% selected from rare earth oxide, phosphorous oxide, aluminium oxide-silicon oxide one or more oxides or
Its predecessor.
10. preparation method according to claim 9, it is characterised in that the catalytic cracking catalyst contains 0.2~6%
Selected from rare earth oxide, phosphorous oxide, aluminium oxide-silicon oxide one or more oxides or its predecessor.
11. preparation method according to claim 10, it is characterised in that the catalytic cracking catalyst contains 0.2~
2% rare earth oxide or rare earth oxide predecessor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410827885.2A CN105772074B (en) | 2014-12-25 | 2014-12-25 | A kind of preparation method of catalyst for heavy oil catalytic cracking |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410827885.2A CN105772074B (en) | 2014-12-25 | 2014-12-25 | A kind of preparation method of catalyst for heavy oil catalytic cracking |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105772074A CN105772074A (en) | 2016-07-20 |
| CN105772074B true CN105772074B (en) | 2018-07-13 |
Family
ID=56388646
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410827885.2A Active CN105772074B (en) | 2014-12-25 | 2014-12-25 | A kind of preparation method of catalyst for heavy oil catalytic cracking |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105772074B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108262056A (en) * | 2016-12-30 | 2018-07-10 | 中国石油天然气股份有限公司 | A kind of adjustable catalytic cracking catalyst of pore volume and preparation method thereof |
| CN108264924B (en) * | 2016-12-30 | 2021-04-30 | 中国石油天然气股份有限公司 | Hydrocarbon catalytic cracking method for increasing gasoline yield |
| CN108404897B (en) * | 2017-02-10 | 2021-03-09 | 中国石油天然气股份有限公司 | Heavy oil hydrogenation catalyst carrier, preparation method thereof, catalyst using heavy oil hydrogenation catalyst carrier and preparation method of catalyst |
| CN108686702B (en) * | 2018-06-06 | 2021-03-09 | 一重集团大连工程建设有限公司 | Fluidized bed coal tar hydrotreating-hydrocracking composite catalyst and preparation method thereof |
| CN112427010B (en) * | 2020-11-06 | 2023-05-23 | 盐城工学院 | HZSM-5 molecular sieve gas adsorbent synthesized by attapulgite, and preparation method and application thereof |
| CN113041989B (en) * | 2021-03-19 | 2023-05-16 | 润和催化材料(浙江)有限公司 | Sulfur transfer agent with surface rich in alkaline sites and preparation method thereof |
| CN113101967B (en) * | 2021-04-15 | 2022-08-30 | 青岛中瑞泰丰新材料有限公司 | C5 and/or C9 petroleum resin two-stage hydrofining catalyst and preparation method and application thereof |
| CN115888799A (en) * | 2021-09-30 | 2023-04-04 | 中国石油化工股份有限公司 | Metal contamination resistant catalyst, preparation and use thereof |
| CN116328819A (en) * | 2021-12-17 | 2023-06-27 | 中国石油天然气股份有限公司 | Preparation method of low-coke catalytic cracking catalyst |
| CN115069296B (en) * | 2022-07-18 | 2023-12-12 | 青岛惠城环保科技集团股份有限公司 | Preparation method of catalytic cracking catalyst for increasing yield of high-quality needle coke raw material |
| CN116273142A (en) * | 2023-03-06 | 2023-06-23 | 青岛惠城环保科技集团股份有限公司 | Preparation method of diesel catalytic cracking catalyst for increasing yield |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1311288A (en) * | 2000-03-03 | 2001-09-05 | 中国石油化工集团公司 | Process for preparing catalystic cracking catalyst |
| CN101134905A (en) * | 2006-08-30 | 2008-03-05 | 中国石油天然气股份有限公司 | Method for improving solid content of catalytic cracking catalyst slurry |
| CN103031062A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Peptizing aluminum adhering agent and preparation method of peptizing aluminum adhering agent, catalytic cracking catalyst and preparation method of catalytic cracking catalyst |
| CN103028437A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Peptizing aluminum adhering agent, preparation method of peptizing aluminum adhering agent, catalytic cracking catalyst and preparation method of catalytic cracking catalyst |
-
2014
- 2014-12-25 CN CN201410827885.2A patent/CN105772074B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1311288A (en) * | 2000-03-03 | 2001-09-05 | 中国石油化工集团公司 | Process for preparing catalystic cracking catalyst |
| CN101134905A (en) * | 2006-08-30 | 2008-03-05 | 中国石油天然气股份有限公司 | Method for improving solid content of catalytic cracking catalyst slurry |
| CN103031062A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Peptizing aluminum adhering agent and preparation method of peptizing aluminum adhering agent, catalytic cracking catalyst and preparation method of catalytic cracking catalyst |
| CN103028437A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Peptizing aluminum adhering agent, preparation method of peptizing aluminum adhering agent, catalytic cracking catalyst and preparation method of catalytic cracking catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105772074A (en) | 2016-07-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105772074B (en) | A kind of preparation method of catalyst for heavy oil catalytic cracking | |
| CN101829592B (en) | Preparation method of fluidizing, catalyzing and cracking catalyst with high solid content | |
| CN101134905B (en) | Method for improving solid content of catalytic cracking catalyst slurry | |
| CN101134906B (en) | Method for improving solid content of catalytic cracking catalyst slurry | |
| JP6584411B2 (en) | FCC catalyst composition containing boron oxide | |
| CN1854258A (en) | Cracking catalyst | |
| JP5911446B2 (en) | Method for producing catalytic cracking catalyst of hydrocarbon oil | |
| TWI650176B (en) | Fcc catalyst compositions containing boron oxide and phosphorus | |
| JP3949778B2 (en) | Catalytic cracking catalyst | |
| JP7064484B2 (en) | The process of degluing alumina for a flow catalyst | |
| CN105728014B (en) | A kind of preparation method of catalytic cracking catalyst | |
| US8940156B2 (en) | Thermochemical structuring of matrix components for FCC catalysts | |
| KR20080112241A (en) | Cracking catalyst, process for preparation thereof, and process for catalytic cracking of hydrocarbon oil | |
| CN103301870A (en) | Preparation method for catalytic cracking cocatalyst | |
| JP2017506270A (en) | Boron oxide in FCC method | |
| CN102430422B (en) | Catalytic cracking catalyst for producing low-carbon olefin and application thereof | |
| CN104549419B (en) | The method of catalyst for heavy oil catalytic cracking and preparation method thereof and RFCC | |
| JP4115843B2 (en) | Zeolite-based catalyst with extremely high dynamic conversion activity | |
| CN103861636A (en) | Heavy oil catalytic cracking catalyst for enhancing diesel oil yield and preparation method of catalyst | |
| CN105728029A (en) | Anti-nickel cracking catalyst | |
| CN1312255C (en) | Process for preparing cracking catalyst for hydrocarbons containing molecular sieves | |
| CN101745416B (en) | Catalytic cracking catalyst and preparation method thereof | |
| CN101733141B (en) | Catalytic cracking catalyst and preparation method thereof | |
| CN1332765C (en) | Process for preparing cracking catalyst for hydrocarbons containing molecular sieves | |
| CN1291788C (en) | Process for preparing cracking catalyst for hydrocarbons containing molecular sieves |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |