CN102233281B - Preparation of active carrier and application thereof - Google Patents
Preparation of active carrier and application thereof Download PDFInfo
- Publication number
- CN102233281B CN102233281B CN 201010160493 CN201010160493A CN102233281B CN 102233281 B CN102233281 B CN 102233281B CN 201010160493 CN201010160493 CN 201010160493 CN 201010160493 A CN201010160493 A CN 201010160493A CN 102233281 B CN102233281 B CN 102233281B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- weight
- molecular sieve
- roasting
- active carrier
- 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
Landscapes
- Catalysts (AREA)
Abstract
A preparation method of an active carrier comprises the following steps of: (1) mixing waste residue of a catalyst and an aluminium source and/or a silicon source, roasting, or roasting after drying; (2) carrying out ion exchange between the material obtained from Step (1) and sodium salt, followed by washing; (3) carrying out a reaction between the material obtained from Step (2) and a molecular sieve crystallization synthesis system, and recycling the reaction product to obtain the active carrier. The active carrier is used to prepare a catalytic cracking catalyst, and can improve the activity of the catalyst and reduce the coke content.
Description
Technical field
The present invention relates to a kind of method of utilizing of catalyst waste slag, relate to furtherly a kind of method that is prepared active carrier and catalytic cracking catalyst by catalyst waste slag.
Background technology
For example in the production process of Cracking catalyst, can produce a large amount of industrial solid waste residues at petroleum refining catalyst, the main component of these solid slags comprises SiO
2, Al
2O
3, RE
2O
3, Na
2O and Fe
2O
3Deng, and contain a small amount of Cl
-, SO
4 2-, F
-, Ca
2+, Mg
2+, P, As, Pb etc., these compositions may exist with various ways such as catalyst granules, molecular sieve such as various ZSM-5 and Y molecular sieve, silicon (aluminium) glue, clays.At present, catalyst manufacturer adopts the method for landfill to process these waste residues mostly, and this is not only to environment, and is the serious waste to resource.
CN1299778A discloses a kind of preparation method of A type molecular sieve, the catalyst plant waste residue of siliceous and/or aluminium is added the water making beating, add or do not add other silicon source, then to wherein adding aluminate and mixing, the basicity that feeds intake with acid aluminium salt, acid or alkali adjustment again makes the mole composition of last gained reactant mixture meet (2.0～4.0) Na
2O: Al
2O
3: (1.8～3.5) SiO
2: (80～200) H
2The proportioning of O, the wherein Al in the waste residue
2O
3Account for the total Al of mixed material
2O
30～45 heavy % of amount, the SiO in the waste residue
2Account for the total SiO of mixed material
25～100 heavy % of amount; Then with the gained reactant mixture according to a conventional method hydrothermal crystallizing obtain A type molecular sieve.
CN1406868A discloses a kind of lattice constant more than or equal to the preparation method of the low silica-alumina ratio X molecular sieve of 2.50 nanometers.Comprise: according to the chemical composition of waste residue and/or mother liquor, in catalyst plant waste residue and/or mother liquor, add NaOH and potassium hydroxide mixed base and waterglass and/or aluminium source according to required charge ratio, and mix, make total mole of composition of gained reactant mixture meet (4.0～6.0) Na
2O: (1.0～2.5) K
2O: Al
2O
3: (1.0～3.0) SiO
2: (50～250) H
2The proportioning of O, the wherein Al in waste residue and the mother liquor
2O
3Account for the total Al of mixed material
2O
30～50 heavy % of amount, the SiO in waste residue and the mother liquor
2Account for the total SiO of mixed material
215～100 heavy % of amount, the alkali in waste residue and the mother liquor accounts for 0～45% of total alkali content, with the gained mixture 20～50 ℃ of lower ageings 1～4 day.
CN1245140A discloses a kind of method for preparing Y zeolite, and the method is comprised of the following step: (1) prepares directed agents according to the method for preparing directed agents that adopts in the conventional NaY molecular sieve preparation method; (2) with this directed agents and waterglass, contain SiO
2And Al
2O
3Waste residue, aluminium salt and/or sodium metaaluminate mix, and adjust the basicity of mixture, the mole of gained reactant mixture is formed meets (1.5～4.5) Na
2O: Al
2O
3: (5.5～12) SiO
2: (I00～300) H
2The proportioning of O, the wherein Al in the directed agents
2O
3Account for the total Al of said mixture
2O
32～8%, preferably 3.5～6.0% of amount; Al in the waste residue
2O
3Account for the total Al of said mixture
2O
30～60%, preferably 0～55% of amount; SiO2 in the waste residue accounts for the total SiO of said mixture
215～50%, preferably 20～40% of amount; Na wherein
2O represents the basicity of mixture, and it does not comprise the part that is neutralized by acid; (3) with (2) gained mixture hydrothermal crystallizing and reclaim product according to a conventional method.
CN1362366A also discloses a kind of preparation method of small cell Y type molecular sieve, it is characterized in that the method is that raw material is prepared parent NaY molecular sieve with the catalyst plant waste residue; This NaY molecular sieve is taken off sodium according to conventional method process the Na that makes molecular sieve
2O content is less than 6 % by weight; Gained is taken off molecular sieve behind the sodium, and to make the structure cell of molecular sieve be contracted to lattice constant according to conventional method be 2.440～2.463nm.
CN1299857A discloses a kind of preparation method of catalyst for cracking petroleum hydrocarbons, the method comprises: be the catalyst plant waste residue of the siliceous and/or aluminium of 10～70 % by weight with solid content, join in the catalyst prepared slarry that contains molecular sieve and carrier according to the preparation of the method for prior art, to replace a part of carrier wherein; After fully mixing, with gained slurry mixture spray-drying according to a conventional method; In the end in the gained slurry mixture, the addition of said waste residue is counted 5～25 % by weight of whole catalyst butt gross weight by butt weight.
Use the waste residue of catalyst preparation to prepare molecular sieve or as catalyst carrier, do not process the impurity that contains in the catalyst waste slag but relate in the above prior art.
Summary of the invention
One of the technical problem to be solved in the present invention provides a kind of method of utilizing catalyst waste slag to prepare active carrier, and the other technical problem that the present invention will solve provides a kind of method that is prepared Cracking catalyst by this active carrier.
The invention provides a kind of preparation method of active carrier, comprising:
(1) catalyst waste slag is mixed with aluminium source and/or silicon source and carry out composition regulation, then will carry out roasting after the roasting of gained mixture or the drying;
(2) material that step (1) is obtained contacts with sodium salt and carries out ion-exchange, then washing;
(3) material that step (2) is obtained reacts in the crystallization synthetic system, and will react afterproduct and reclaim and to obtain active carrier material.
The present invention also provides a kind of active carrier material that is obtained by said method.
The present invention also provides a kind of preparation method of Cracking catalyst, comprising:
(1) prepares active carrier material according to active carrier preparation method provided by the invention;
(2) active carrier material that step (1) is obtained and molecular sieve and/or matrix making beating, then spray-drying obtains the catalyst powder particle;
The present invention also provides a kind of Cracking catalyst that is obtained by production of cracking catalyst provided by the present invention.
Active material preparation method provided by the invention utilizes catalyst waste slag as synthesis material, utilizes method to compare with existing catalyst waste slag, has the following advantages:
(1) in catalyst waste slag, replenishes in advance aluminium source and/or silicon source, waste residue is carried out composition regulation, be conducive to stablize the sial composition of waste residue, overcome catalyst waste slag and form the large problem of fluctuation;
(2) to carrying out ion-exchange treatment after the waste residue roasting behind the composition regulation, can reduce or eliminate because the impurity that contains in the catalyst waste slag (F for example
-, Ca
2+, Mg
2+, P, As, Pb etc.) to the harmful effect of institute's synthetic material performance;
(3) catalyst waste slag after will processing carries out the crystallization synthetic reaction, make the active carrier material with certain molecular sieve content, this material can be used as carrier or active component is used for the catalyst preparation, be unexpectedly, as the catalytic cracking catalyst carrier, can improve the cracking activity of catalyst, it is selective to improve coke.Cracking catalyst provided by the invention is applicable to hydrocarbon oil catalytic cracking, is particularly useful for RFCC.
The specific embodiment
Among the preparation method of active carrier provided by the invention, with aluminium source and/or silicon source the composition of catalyst waste slag is regulated first, formed the impact that fluctuation causes to reduce catalyst waste slag.Wherein the consumption in catalyst waste slag, aluminium source and/or silicon source makes that the weight ratio of silica and aluminium oxide is 0.5～2: 1 in the mixture that obtains, and preferred 0.7～1.5: 1 more preferably 0.8～1.2: 1.The consumption in silicon source and/or aluminium source makes catalyst waste slag be not less than 70 % by weight (take the butt weight of mixture as benchmark) through the total content of aluminium oxide and silica in the catalyst waste slag mixture that obtains behind the composition regulation, roasting, is preferably 75～95 % by weight.When the content of aluminium oxide in the catalyst waste slag is higher, can add the silicon source, make that the weight ratio of silica and aluminium oxide is 0.5～2: 1 in the catalyst waste slag mixture after the adjustment, otherwise then can add the aluminium source, make that the weight ratio of silica and aluminium oxide is 0.5～2: 1 in the mixture that obtains after the adjustment.Described aluminium source is selected from one or more in aluminium salt, aluminium oxide, hydrated alumina, alumina gel and the aluminium colloidal sol; Described aluminium salt is aluminium chloride, aluminum sulfate, aluminum nitrate, sodium metaaluminate for example; Described aluminium oxide is gama-alumina, η-aluminium oxide, θ-aluminium oxide, χ-aluminium oxide for example; Described hydrated alumina is boehmite, the hydrated alumina that has a diaspore structure hydrated alumina, have gibbsite structure hydrated alumina, have the bayerite structure for example; Preferred aluminium source is aluminum sulfate; Described silicon source is selected from one or more in silicate, porous silica, Ludox and the silicon gel; Described silicate is sodium silicate, KP1 for example, and described porous silica silochrom, Kiselgel A, chromatographic silica gel, described Ludox can be that alkaline silica sol also can be acidic silicasol.Also can in catalyst waste slag, introduce simultaneously the aluminium source and composition regulation is carried out in the silicon source, for example introduce Alusil or introduce waterglass simultaneously and aluminum sulfate is regulated.Mixture behind the adjustment of formula can directly carry out roasting, and also then drying carries out roasting first, and sintering temperature is 600～800 ℃, and roasting time is 1～3 hour.When comprising drying steps, described drying can be oven dry, pneumatic conveying drying or expansion drying, these drying means are well known to those skilled in the art, for example described oven dry can be 100～150 ℃ of lower dry sufficiently long times, preferred 0.5～24 hour, described expansion drying can be to carry out drying under leaving air temp is 100～150 ℃ condition.
Among the preparation method of active carrier provided by the invention, catalyst waste slag exchanges with sodium salt after regulating composition, roasting (or dry roasting) with aluminium source and/or silicon source.The weight ratio of the material that the sodium salt consumption (in sodium oxide molybdena) described in the step (2) and step (1) obtain is for being not less than 0.2: 10, preferred 0.2～2: 10, more preferably 1～1.5: 10, too high sodium salt consumption can be applicable to the present invention, but can increase processing cost, cause the waste of sodium salt.Preferred described exchange comprises: the sodium salt solution that the material that step (1) is obtained is 0.1～10 % by weight with sodium oxide molybdena concentration, be preferably 1～5 heavy amount % contacts, and the time of contact is preferably 0.5～3 hour, and the temperature of contact is 50～90 ℃.Exchange and wash after complete, with sodium ion and the metal ion that the exchanges rare earth ion for example for example of the free metal ion in the flush away material, described washing can be adopted decationized Y sieve water, distilled water or deionized water.The total content of silica and aluminium oxide preferably is not less than 80 % by weight (the catalyst waste slag butt weight after exchange, the washing is as benchmark) in the catalyst waste slag after exchange, the washing, content in oxide metal impurities (metal beyond the aluminium) preferably is no more than 8 % by weight, more preferably no more than 5 % by weight.
Among the preparation method of active carrier provided by the invention, the material that step (2) is obtained carries out crystallization in the crystallization synthetic system.Described crystallization synthetic system is preferably the synthetic system of NaY molecular sieve, this system has the proportioning of the sodium oxide molybdena, aluminium oxide, silica and the water that are suitable for the NaY Zeolite synthesis, wherein the part component source is from NaY Zeolite synthesis directed agents, and the mole proportion optimization that has in the NaY Zeolite synthesis system of the present invention is 0.3～1Na
2O: Al
2O
3: 8～15SiO
2: 190～280H
2O comprises silica and aluminium oxide that material that step (2) obtains is introduced during wherein silica and aluminium oxide form.When described synthetic system is the synthetic system of NaY molecular sieve, the described material that step (2) is obtained carries out crystallization in the crystallization synthetic system, comprising that material, NaY molecular sieve guiding agent, silicon source preferred water glass, water that step (2) is obtained mix, is 80-120 ℃ of reaction 10-55h in temperature then; Wherein the consumption of the material, NaY molecular sieve guiding agent, silicon source and the water that obtain of step (2) makes the mole of the mixture that obtains consist of 0.3～1Na
2O: Al
2O
3: 8～15SiO
2: 190～280H
2O; Described NaY molecular sieve guiding agent is NaY Zeolite synthesis directed agents commonly used, can be according to existing method preparation, and its mole consists of 15～17Na usually
2O: Al
2O
3: 14～16SiO
2: 200～350, the aluminium oxide that is derived from directed agents in the synthetic system accounts for the 0.1-10 % by weight of aluminium oxide total amount in the system, more preferably 1-8 % by weight.
After crystallization finishes, the reactant mixture recovery is obtained active carrier material.Described recovery comprises the step with the filtration of the product behind the crystallization, washing, drying, perhaps also comprises the step of modification (for example carrying out ion-exchange, roasting with rare earth and/or ammonium ion).Described filtration, washing, drying, modification, roasting can be adopted prior art, and these technology are well known to those skilled in the art.For example, described drying can be oven dry or pneumatic conveying drying, and dry temperature can be 100～200 ℃; Described washing can adopt deionized water to wash, flush away free sodium ion wherein; Described modification can adopt the mode of ion-exchange to carry out, when for example synthesizing according to the synthetic system of NaY molecular sieve, and can be according to the method for modifying modification of NaY molecular sieve; Described roasting can be carried out under 450～650 ℃ 1～10 hour.
Among the preparation method of catalytic cracking catalyst provided by the invention, will be according to active carrier material and molecular sieve and/or the matrix making beating of active carrier preparation method preparation of the present invention, then spray-drying obtains catalyst powder.Wherein, described molecular sieve is Cracking catalyst preparation molecular sieve commonly used, for example Y zeolite, five-membered ring structure molecular sieve, described Y zeolite is one or more in USY molecular sieve, REY molecular sieve, HY molecular sieve, REHY molecular sieve and the REUSY molecular sieve for example, and described five-membered ring structure molecular sieve is for example ZSM-5 molecular sieve, in the transition metal modified ZSM-5 molecular sieve one or more of phosphorus modification of HZSM-5 molecular sieve, element modified ZSM-5 molecular sieve for example.In described matrix such as kaolin, boehmite, Ludox, aluminium colloidal sol, kaolin, aluminium oxide, rectorite, the waterglass etc. one or more.Can also comprise catalyst powder particle washing that spray-drying is obtained, dry step or also further comprise the step of roasting.Described washing, drying and roasting can be according to existing methods, and for example with the ammonium sulfate washing, with the deionized water washing, described drying can adopt pneumatic conveying drying, and the temperature of described roasting is 450～650 ℃, and the time is 1～5 hour.
In the catalytic cracking catalyst provided by the invention, preferred, comprise the described active carrier of 5～50 % by weight, 15～45 % by weight molecular sieves, 20～55 % by weight matrix; SiO in the described active carrier
2With Al
2O
3Mol ratio is 8～15: 1, Na
2O and Al
2O
3Mol ratio is generally 0.3～1 for being no more than 1: 1: 1.
Embodiment 1
Catalyst waste slag is taken from China Petrochemical Industry's catalyst asphalt in Shenli Refinery, and solid content is 21.25 % by weight, and the percentage composition of butt weight is Na
2O is that 4.9%, MgO is 1.6%, SiO
2Be 29.1%, Al
2O
3Be 44.1%, Re
2O
3Be 2.8%, SO
4 2-Be 14.1%, Fe
2O
3Be 0.62%, Cl
-Be 0.95%.Get described catalyst waste slag 60kg, deionized water 8kg, waterglass (SiO
2Concentration 28.5 % by weight, modulus 3.0, Red Star water glass plant, Beijing product) 3kg mixes making beating, and with above-mentioned slurries expansion drying (260～280 ℃ of the EATs of expansion drying, 110～130 ℃ of leaving air temps), then 800 ℃ of lower roastings 2 hours, obtain the catalyst waste slag after the roasting.Catalyst waste slag after the 10kg roasting and 1kg sodium chloride are joined in the 100kg deionized water, 70 ℃ of lower stirrings 0.5 hour, then filter, wash the flush away free metal ion with deionized water, the catalyst waste slag after final drying obtains processing, its butt weight consists of Na
2O is that 4.6%, MgO is 1.1%, SiO
2Be 43.6%, Al
2O
3Be 39.3%, Re
2O
3Be 1.5%, SO
4 2-Be 8.5%, Fe
2O
3Be 0.3%, Cl
-Be 0.4%.
Low alkali aluminium acid sodium solution (is contained Al
2O
3: 11.3 % by weight, Na
2The O:15.8 % by weight) 0.9kg, sodium hydroxide solution (Na
2O content 23.3 % by weight) 2.5kg and water glass solution (contain SiO
2: 28.4 % by weight, Na
2The O:8.9 % by weight) 2kg mixes, and stirs, and makes directed agents in 4 hours 40 ℃ of lower wearing out.In reactor, add deionized water 12.8kg, in stirring the lower above-mentioned directed agents 2.7kg of adding, then add water glass solution and (contain SiO
2: 28.4 % by weight, Na
2The O:8.9 % by weight) then 7kg adds the catalyst waste slag 3.9kg after the processing that present embodiment obtains, and stirs 10 minutes, with the reactor sealing, in 100 ℃ of lower crystallization 24 hours, obtains crystallization product.With the crystallization product filtration, with deionized water washing, drying, obtain active carrier material S1, the Y zeolite content that records among the S1 is 27%; (described molecular sieve content (degree of crystallinity) adopts the methods analyst of " Petrochemical Engineering Analysis method (RIPP test method) " (Yang Cuiding, Gu Kanying volume, 1990, Science Press) to obtain)
With 3.8kg DASY2.0 molecular sieve (molecular sieve solid content 78 % by weight, content of rare earth 2 % by weight, China Petrochemical Industry's catalyst asphalt in Shenli Refinery product), 4.1kg active carrier S (solid content 98 % by weight), 4.2kg boehmite slurries (alumina content 12 % by weight), 1.2kg Kaolin of Suzhou (solid content 84 % by weight, Suzhou China Kaolin Co., Ltd produces), 7.0kg aluminium colloidal sol (alumina content 21.5 % by weight) and 20kg deionized water are mixed making beating, be prepared into the catalyst colloid, the catalyst colloid is carried out spray-drying, ammonium chloride solution washing with concentration 3 % by weight, then wash free sodium ion in the catalyst off with deionized water, filter, dry, 500 ℃ of lower roastings 2 hours, finally obtain the Cracking catalyst product, be designated as A.
Embodiment 2
With 3.8kg DASY2.0 molecular sieve (molecular sieve solid content 78 % by weight, content of rare earth 2 % by weight, China Petrochemical Industry's catalyst asphalt in Shenli Refinery product), weight 3.2kg active carrier S1 (98 % by weight), 8.4kg boehmite (12 % by weight), 2.4kg Kaolin of Suzhou (84 % by weight), 4.7kg aluminium colloidal sol (21.5 % by weight) and 18kg deionized water are mixed making beating, be prepared into the catalyst colloid, the catalyst colloid is carried out spray-drying obtain the catalyst powder particle, the catalyst powder particle is washed the free sodium ion of removing wherein with deionized water, filter, dry, 500 ℃ of lower roastings 2 hours, finally obtain the Cracking catalyst product B.
Embodiment 3
With 3.8kg DASY2.0 molecular sieve (molecular sieve solid content 78 % by weight, content of rare earth 2 % by weight, China Petrochemical Industry's catalyst asphalt in Shenli Refinery product), 2.0kg active carrier S1 (98 % by weight), 16.8kg boehmite (12 % by weight), 2.4kg Kaolin of Suzhou (84 % by weight), 4.7kg aluminium colloidal sol (21.5 % by weight) and 11kg deionized water are mixed making beating, be prepared into the catalyst colloid, the catalyst colloid is carried out spray-drying, and the ammonium chloride solution with 3% and deionized water wash away the sodium ion in the catalyst, filter, dry, 500 ℃ of lower roastings 2 hours, finally obtain the Cracking catalyst products C.
Embodiment 4
The solid content of catalyst waste slag (taking from China Petrochemical Industry's catalyst asphalt in Shenli Refinery) is 25.6 % by weight, and the percentage composition of butt weight is: Na
2O is that 3.6%, MgO is 1.1%, SiO
2Be 48.2%, Al
2O
3Be 40.8%, Re
2O
3Be 1.4%, SO
4 2-Be 3.5%, Fe
2O
3Be 0.5%, Cl
-Be 0.6%.Get described catalyst waste slag 50kg, deionized water 7.5kg, alumina powder (Al
2O
3Concentration 62 % by weight) 3.0kg mixes making beating, and with above-mentioned slurries expansion drying (temperature is 150～170 ℃ in 260～280 ℃ of the EATs, tower, 110～130 ℃ of leaving air temps), then 700 ℃ of lower roastings 3 hours, obtain the catalyst waste slag after the roasting.Catalyst waste slag after the 10kg roasting and 1.5kg sodium chloride are joined in the 100kg deionized water, 70 ℃ of lower stirrings 0.5 hour, then filter, (temperature of washing water is 70 ℃ with deionized water drip washing filter cake, water consumption is 20 times of waste residue butt weight) with the flush away free metal ion, catalyst waste slag after final drying obtains processing, its butt weight consists of Na
2O is that 3.9%, MgO is 0.7%, SiO
2Be 43.2%, Al
2O
3Be 46.6%, Re
2O
3Be 0.9%, SO
4 2-Be 2.7%, Fe
2O
3Be 0.4%, Cl
-Be 0.5%.
Low alkali aluminium acid sodium solution (is contained Al
2O
3: 11.3 % by weight, Na
2The O:15.8 % by weight) 0.9kg, sodium hydroxide solution (Na
2O content 23.3 % by weight) 2.5kg and water glass solution (contain SiO
2: 28.4 % by weight, Na
2The O:8.9 % by weight) 2kg mixes, and stirs, and makes directed agents in 4 hours 40 ℃ of lower wearing out.In reactor, add deionized water 13.5kg, in stirring the lower above-mentioned directed agents 3.0kg of adding, then add waterglass and (contain SiO
2: 28.4 % by weight, Na
2The O:8.9 % by weight) then 6.8kg adds the catalyst waste slag 4.2kg after the processing that present embodiment obtains, and stirs 10 minutes, with the reactor sealing, in 100 ℃ of lower crystallization 24 hours, obtains crystallization product.Crystallization product is filtered, uses deionized water drip washing filter cake (60 ℃ of water temperatures, consumption are 15 times of filter cake butt weight), drying, obtain active carrier material, be designated as S2, the Y zeolite content that records among the S2 is 33%; (described molecular sieve content (degree of crystallinity) adopts the methods analyst of " Petrochemical Engineering Analysis method (RIPP test method) " (Yang Cuiding, Gu Kanying volume, 1990, Science Press) to obtain)
With 3.8kg DASY2.0 molecular sieve (molecular sieve solid content 78 % by weight, content of rare earth 2 % by weight, China Petrochemical Industry's catalyst asphalt in Shenli Refinery product), 4.0kg active carrier S2 (solid content 99 % by weight), 4.2kg boehmite slurries (alumina content 12 % by weight), 1.2kg Kaolin of Suzhou (solid content 84 % by weight, Suzhou China Kaolin Co., Ltd produces), 7.0kg aluminium colloidal sol (alumina content 21.5 % by weight) and 20kg deionized water are mixed making beating, be prepared into the catalyst colloid, the catalyst colloid is carried out spray-drying obtain the catalyst powder particle, be that the ammonium chloride solution (the ammonium chloride solution consumption is 10 times of catalyst powder particle butt weight) of 3 % by weight mixes with catalyst powder particle and concentration, in 50 ℃ of lower stirrings 20 minutes, filter, with 50 ℃ of deionized water drip washing (the deionized water consumption is 15 times of filter cake butt weight), filter, dry, 500 ℃ of lower roastings 2 hours, finally obtain Cracking catalyst product D.
Comparative Examples 1
With 3.8kg DASY2.0 molecular sieve (molecular sieve solid content 78 % by weight, content of rare earth 2 % by weight, China Petrochemical Industry's catalyst asphalt in Shenli Refinery product), 20.8kg boehmite (12 % by weight), 4.8kg Kaolin of Suzhou (84 % by weight), 2.4kg aluminium colloidal sol (21.5 % by weight) and 8.5kg deionized water are mixed making beating, be prepared into the catalyst colloid, the catalyst colloid is carried out spray-drying, and the ammonium chloride solution with 3% and deionized water washing, filter, dry, 500 ℃ of lower roastings 2 hours, finally obtain the Cracking catalyst product E.
Respectively above-mentioned 5 catalyst samples are carried out micro-activity evaluation and catalyst carbon deposition analysis, (Yang Cuiding, Gu Kanying compile referring to " Petrochemical Engineering Analysis method (RIPP test method) " for the micro-activity evaluation of catalyst sample and carbon distribution analysis, 1990, Science Press).The results are shown in Table 1.
Table 1
| The sample title | A | B | C | D | E |
| Micro-activity/% | 90 | 88 | 89 | 92 | 85 |
| Catalyst carbon deposition/% by weight | 1.5 | 1.8 | 2.0 | 1.6 | 3.2 |
By as seen from Table 1, be used for catalytic cracking catalyst with active carrier provided by the invention and can improve the activity of catalyst, and can reduce the coke content on the catalyst.
Claims (13)
1. the preparation method of an active carrier may further comprise the steps:
(1) catalyst waste slag is mixed with aluminium source and/or silicon source and carry out composition regulation, then roasting or dry roasting, sintering temperature is 600～800 ℃, roasting time is 1～3 hour, in the mixture that aluminium source and/or silicon source and catalyst waste slag form, the weight ratio of silica and aluminium oxide is 0.5～2: 1;
(2) material that step (1) is obtained contacts with sodium salt and carries out ion-exchange, washing;
(3) material that step (2) is obtained reacts in the Crystallization of Zeolite synthetic system, will react afterproduct and reclaim.
2. in accordance with the method for claim 1, it is characterized in that in the mixture that aluminium source and/or silicon source and catalyst waste slag form in the step (1), the weight ratio of silica and aluminium oxide is 0.8～1.2: 1.
3. in accordance with the method for claim 1, it is characterized in that the weight ratio of described silica and aluminium oxide is 0.7～1.5: 1.
4. according to each described method of claim 1～3, it is characterized in that, after the mixture roasting that aluminium source and/or silicon source and catalyst waste slag form, the butt weight of the mixture after the roasting is as benchmark, and the total content of silica and aluminium oxide is not less than 70 % by weight.
5. in accordance with the method for claim 1, it is characterized in that the temperature of roasting is 700～800 ℃ in the step (1), roasting time is 2～3 hours.
6. in accordance with the method for claim 1, it is characterized in that in the step (2), the weight ratio of the material that obtains take sodium salt and the step (1) of sodium oxide molybdena is as 0.2～2: 10.
7. in accordance with the method for claim 5, it is characterized in that described contact contacts 0.5～3 hour with sodium salt solution in 50～90 ℃ of temperature for the material that step (1) is obtained, the concentration of sodium oxide molybdena is 1～10 % by weight in the sodium salt solution.
8. according to each described method of claim 1～7, it is characterized in that described Crystallization of Zeolite synthetic system is the synthetic system of NaY molecular sieve.
9. in accordance with the method for claim 8, it is characterized in that, the described material that step (2) is obtained carries out crystallization in the crystallization synthetic system, comprising that material, NaY molecular sieve guiding agent, waterglass and water that step (2) is obtained mix, is 80-120 ℃ of reaction 10-55h in temperature then;
Wherein the consumption of the material, NaY molecular sieve guiding agent, waterglass and the water that obtain of step (2) makes the mole of the mixture that obtains consist of 0.3～1Na
2O: Al
2O
3: 8～15SiO
2: 190～280H
2O.
10. an active carrier material is characterized in that, by each described method preparation of claim 1～9.
11. the preparation method of a catalytic cracking catalyst may further comprise the steps:
(1) prepares active carrier material according to each described method of claim 1～9;
(2) active carrier material that step (1) is obtained mixes making beating with molecular sieve and/or matrix, and then spray-drying obtains the catalyst powder particle.
12. a catalytic cracking catalyst is characterized in that, described catalytic cracking catalyst is by the described method preparation of claim 11.
13., it is characterized in that described catalytic cracking catalyst comprises the active carrier of 5～50 % by weight according to the described catalytic cracking catalyst of claim 12,15～45 % by weight molecular sieves, 20～55 % by weight matrix.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010160493 CN102233281B (en) | 2010-04-30 | 2010-04-30 | Preparation of active carrier and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010160493 CN102233281B (en) | 2010-04-30 | 2010-04-30 | Preparation of active carrier and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102233281A CN102233281A (en) | 2011-11-09 |
| CN102233281B true CN102233281B (en) | 2013-04-24 |
Family
ID=44884683
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010160493 Active CN102233281B (en) | 2010-04-30 | 2010-04-30 | Preparation of active carrier and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102233281B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106495182A (en) * | 2016-10-27 | 2017-03-15 | 湖南理工学院 | A kind of preparation method of zeolite L molecular sieve |
| CN112570003B (en) * | 2020-12-21 | 2022-10-21 | 湖南长科诚享石化科技有限公司 | Catalytic cracking catalyst and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4226837A (en) * | 1976-11-11 | 1980-10-07 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler | Process for converting silicon dioxide containing waste flue dust to crystalline zeolitic molecular sieves of type Y with a Faujasite structure |
| US4503023A (en) * | 1979-08-14 | 1985-03-05 | Union Carbide Corporation | Silicon substituted zeolite compositions and process for preparing same |
| CN1245140A (en) * | 1998-08-14 | 2000-02-23 | 中国石油化工集团公司 | Process for preparing Y-type molecular sieve |
| CN1299778A (en) * | 1999-12-13 | 2001-06-20 | 中国石油化工集团公司 | Preparation of A-type zeolite |
| CN1362366A (en) * | 2001-01-04 | 2002-08-07 | 中国石油化工股份有限公司 | Prepn of small cell Y-zeolite |
-
2010
- 2010-04-30 CN CN 201010160493 patent/CN102233281B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4226837A (en) * | 1976-11-11 | 1980-10-07 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler | Process for converting silicon dioxide containing waste flue dust to crystalline zeolitic molecular sieves of type Y with a Faujasite structure |
| US4503023A (en) * | 1979-08-14 | 1985-03-05 | Union Carbide Corporation | Silicon substituted zeolite compositions and process for preparing same |
| CN1245140A (en) * | 1998-08-14 | 2000-02-23 | 中国石油化工集团公司 | Process for preparing Y-type molecular sieve |
| CN1299778A (en) * | 1999-12-13 | 2001-06-20 | 中国石油化工集团公司 | Preparation of A-type zeolite |
| CN1362366A (en) * | 2001-01-04 | 2002-08-07 | 中国石油化工股份有限公司 | Prepn of small cell Y-zeolite |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102233281A (en) | 2011-11-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100389067C (en) | ZSM-5 type molecular sieve and method for preparing the same | |
| CN101249968B (en) | Method for synthesizing Beta molecular sieve by organic-free template | |
| CN102247880B (en) | In situ crystallized cracking catalyst and preparation method thereof | |
| CN100429149C (en) | Production for synthesizing high-content NaY molecular sieve from kaolin atomized microball | |
| CN110523428B (en) | Catalytic cracking catalyst containing NaY molecular sieve composite material and preparation method thereof | |
| CN101767034B (en) | Preparation method of catalysis material containing ZSM-5/Y type composite molecular sieve | |
| CN102049291B (en) | Hydrocarbon catalytic cracking catalyst and preparation method thereof | |
| CN102896000B (en) | Method for utilizing residues of catalyst production | |
| CN101767026B (en) | Preparation method of catalysis material containing Y type molecular sieve | |
| CN102553630B (en) | High- silica alumina ratio small- crystal grain Y zeolite catalytic cracking catalyst and preparation method thereof | |
| CN103055917B (en) | Preparation method of catalytic cracking catalyst | |
| CN105728015A (en) | Comprehensive utilization method for waste residues and waste liquor generated in catalytic cracking catalyst production | |
| US10287172B2 (en) | Preparation method for beta zeolite | |
| CN102502682A (en) | Mordenite preparation method | |
| CN104275205A (en) | Preparation method of catalyst for improving yield of diesel oil produced by catalytic cracking | |
| CN106925335B (en) | Heavy metal resistant catalytic cracking catalyst and preparation method thereof | |
| CN102233281B (en) | Preparation of active carrier and application thereof | |
| CN102442686A (en) | Preparation method of ZSM-5 molecular sieve | |
| CN1150301C (en) | Petroleum hydrocarbon cracking catalyst and its preparation | |
| CN103253683A (en) | Method of in-situ crystallized synthesis of ZSM-5/mordenite compound | |
| CN102895988A (en) | Preparation method for in situ crystallization catalyst | |
| CN102974337B (en) | Catalytic cracking auxiliary agent and preparation method thereof | |
| CN103204519B (en) | Synthetic method of rare-earth silicon-aluminum molecular sieve | |
| CN102847549B (en) | Coal tar hydrocracking catalyst and preparation method thereof | |
| CN101664691B (en) | Method for preparing catalytic cracking bottom oil converting additive |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |