CN1060204C - Laminar column clay microphere cracking catalyst for heavy oil and its preparation - Google Patents
Laminar column clay microphere cracking catalyst for heavy oil and its preparation Download PDFInfo
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Abstract
The present invention relates to a laminated column clay microsphere cracking catalyst of heavy oil for the higher output of gasoline or diesel oil, which comprises: 20 wt%to 90 wt% of laminated column clay, 10 wt% to 40 wt% of bonding agent of which the chemical compositions mainly comprise aluminum oxide, 0 wt% to 40 wt% of Y-type zeolite and 0 wt% to 70 wt% of clay belonging to the kaolinite group. Compared with the existing cracking catalyst which is industrially used and contains rare earth Y or rare earth ultrastable Y-type zeolite, the catalyst has higher heavy oil conversion capability, higher yield of the gasoline or the diesel oil and higher strength and bulk ratio for industrial application.
Description
The invention relates to catalyst for heavy oil catalytic cracking and preparation method thereof.Exactly, the invention relates to a kind of laminar column clay microphere cracking catalyst for heavy oil that is used for voluminous gasoline and diesel oil and preparation method thereof.
Can must have stable catalytic activity for the layer clay microballoon cracking catalyst that industry is adopted simultaneously, to the highly selective of purpose product, qualified intensity and heap ratio, and be easy to industrialization.
Though laminated clay column catalyst of being reported in the existing document and preparation method thereof is constantly improving, but there is such or such problem in varying degrees all the time in they, therefore fail to prepare the laminated clay column catalyst that meets above-mentioned industrial cracking catalyst condition so far, also just fail industrialization so far certainly.
USP4 for example, the layer clay microspherical catalyst of report is with the crosslinked smectite clay of aluminium colloidal sol in 176,090, makes through spray shaping again.Its hydrothermal stability is poor, can only stand 550 ℃ of thermal treatments of 2 hours.Its coke selectivity is also poor, and when transformation efficiency was 82%, coke yield reached 12%.In addition, in preparation process, also exist the filtration difficulty problem of bringing less than 2 μ m owing to the clay particle diameter.
The applicant has developed in CN1007879B a kind ofly has the attrition resistant layer of high hydrothermal stability post rectorite leng cracking catalyst, and wherein adopts the problem that the then crosslinked method of clay microphere has solved filtration difficulty that is prepared into earlier.But the evaluation result by medium-sized this catalyst prod of preparing shows that its catalytic activity is lower than the widely used y-type zeolite cracking catalyst of present industry.Under identical medium-sized riser tube appreciation condition, its transformation efficiency is 62.5%, and the transformation efficiency of industrial REY zeolite catalyst reaches 67.4% (Proceedingof the International Conference on Petroleum Refining and Petrochemical Processing, Vol.3, P1255,1991).For further improving its catalytic activity, the inventor has developed the laminated clay column catalyst with polyvinyl alcohol modification again in ZL CN92114024.X, but does not relate to the catalyzer composition of pressure fuel, voluminous gasoline and diesel oil effectively.
With regard to the preparation method, USP4, having adopted aluminium colloidal sol in 176,090 is linking agent; USP4, having adopted the pseudo-boehmite of mineral acid peptization in 010,116 and USP4,086,187 is binding agent, but never sees the direct peptization pseudo-boehmite of the aluminium colloidal sol of use is arranged as the linking agent of laminated clay column catalyst and the report of binding agent.
Though adopted the crosslinked method for preparing the microballoon cracking catalyst after the first moulding can solve the problem of filtration difficulty among the ZL CN87105686, but when adopting this method prepared layer clay column catalyst in practice, the content of active ingredient will have disadvantageous effect to the intensity of catalyzer when increasing, but and the content of active ingredient can not satisfy the active requirement of commercial catalysts when reducing.That is to say, can not make the microspherical catalyst that satisfies active and requirement of strength simultaneously with this method.
But purpose of the present invention promptly on the basis of above-mentioned prior art, provide a kind of have high ability of residuum conversion and petrol and diesel oil yield, intensity and heap contain layer clay microballoon catalytic cracking catalyst than industrial application.
But another object of the present invention provides the preparation method of the industrial implementation of above-mentioned microspherical catalyst.
The 3rd purpose of the present invention then provides the application of above-mentioned microspherical catalyst in heavy oil fluid catalytic cracking.
Consisting of of layer post microspherical catalyst provided by the invention: the layer clay of 20～90 heavy %; The chemical ingredients of 10～40 heavy % is mainly the binding agent of aluminum oxide; The y-type zeolite of 0～40 heavy %; Kaolin group's clay of 0～70 heavy %.
Wherein said layer clay is the important activity component that this catalyzer transforms heavy oil, and it is with being selected from pseudo-boehmite, metallic aluminium, NH
4The aluminium colloidal sol of one of OH, NaOH, polyvinyl alcohol, fluorocarbon surfactant modification or contain Al
13O
4(OH)
24(H
2O)
12 + 7The hydroxy aluminum mixture be interlayer support thing predecessor's aluminium cross-linked swellable clay.What this swellable clay was meant the various natural or synthetic that comprises rectorite leng and smectite has expansile regular interbed mineral clay or an individual layer mineral clay, is preferably rectorite leng or smectite, preferably rectorite leng.Constitutional features existing detailed description in detail in ZL CN87104718 about rectorite leng.
The binding agent that wherein said chemical ingredients is mainly aluminum oxide is formed by its precursor drying roasting.Its precursor can be to mix the aluminium colloidal sol that the acid that obtained by the aluminium sol-hydrolysis of heating up directly forms behind peptization pseudo-boehmite or the metallic aluminium and the mixture of alumina gel with aluminium colloidal sol and pseudo-boehmite or metallic aluminium; Also can be with adding the colloidalmaterial that forms after the method peptization pseudo-boehmite method of mineral acid; Can also be aluminium colloidal sol and/or the alumina gel that contains polyvinyl alcohol or fluorocarbon surfactant or silicon-aluminum sol.
Wherein said y-type zeolite is the auxiliary activity component that this catalyzer transforms heavy oil, thereby its content can be zero.This y-type zeolite can make the transition through ion-exchange, as rare-earth type, Hydrogen, also can be that the structure cell that obtains after the physics disclosed in the various prior aries and/or chemical means are handled shrinks or the y-type zeolite of non-shrinking modification.
Because mainly consist of layer clay in this catalyzer, itself just can play the effect of carrier in the presence of binding agent, thus just not necessarily essential in this catalyzer as important composition-kaolin group's clay of conventional semi-synthetic carrier.That is to say can be zero as the clay content of carrier.As using kaolin group's clay, be preferably halloysite as carrier.In addition, as the carrier of catalyzer, except that clay, this carrier can also be one or both the mixture that contains in the inorganic oxide of Si, Al, Zr.
Above-mentioned catalyst prod provided by the invention can be by any preparation in following three kinds of methods;
One, hands over the stick method
The characteristics of this method are the linking agents that will be used to prepare layer clay and the binding agent that is used to prepare catalyzer unites two into one, and promptly adopt in the Preparation of catalysts process and can play the friendship stick that crosslinked action can play cohesive action again.This friendship stick component is selected from aluminium colloidal sol intensification hydrolysis gained acid directly peptization pseudo-boehmite or metallic aluminium and aluminium colloidal sol and alumina gel mixture that obtains or other colloidal sol and the gelatinous mass that contains this type of material.In concrete a kind of embodiment, this method can be divided into three following steps;
1. stick is handed in preparation; With aluminium colloidal sol and intend thin water-aluminum hydroxide or aluminum oxide (with Al
2O
3Meter) mixes by 2: 1～5: 1 weight ratio, add an amount of water so that the solid content of gained slurries is 15～30 heavy %, be warming up to 90～100 ℃ and keep the reaction that was hydrolyzed in 0.1～1.5 hour, be cooled to 50～70 ℃ of aging 1～3 hour postcooling then to room temperature.Or aluminium colloidal sol and metal aluminum shot refluxed 6～13 hours at 90～95 ℃, be chilled to room temperature.
2. making beating spray shaping: with the above-mentioned friendship stick that makes and swellable clay, y-type zeolite and carrier component according to 10～40: 20～90: 0～40: 0～70 weight ratio is mixed making beating 1～3 hour, is spray dried to microballoon.
3. aging washing: the microballoon of gained need carry out the aging washing of one or many.
Operational condition when adopting once aging the washing is as follows: with 20～40 times of deionized water NH to the weight of sample
4OH transfers its pH5～6, under 60～75 ℃ microballoon is worn out 0.5～3 hour, filters drying then.
Operational condition when adopting repeatedly aging the washing is as follows.For the first time: with 20～40 times of water NH to example weight
4OH transfers its pH6～9,50～75 ℃ of following washing microballoons 15 minutes, filters.For the second time: with 20～40 times of phosphorus contents to example weight is the phosphoric acid solution NH of 0.03～0.10 heavy %
4OH transfers its pH2～6,50～75 ℃ of following washing microballoons 15 minutes, filters.As desire many washings once, then wash conditions is with for the second time.For the last time: with 20～40 times of water NH to example weight
4OH transfers its pH4～6, washs aging microballoon down at least 15 minutes at 50～75 ℃, filters drying.
Microballoon after the aging washing through 450～650 ℃ of roastings promptly got in 1～3 hour catalyst prod provided by the invention,
Two, improved back crosslinking
The characteristics of this method are that the linking agent with modification behind other component-auxiliary activity component of uncrosslinked swellable clay and catalyzer, carrier, the binding agent mixing moulding is carried out crosslinking reaction.Specifically, this method comprises following three steps:
1. preparation clay microphere: with swellable clay component, carrier component, with the pseudo-boehmite component of hydrochloric acid peptization (with Al
2O
3Meter) and y-type zeolite according to 20～90: 0～70: 10～40: 0～40 weight ratio is mixed and is also made slurries, the spray shaping that solid content is 20～30 heavy %.
2. preparation modified crosslinking agent: commercially available aluminium colloidal sol or the polymerization aluminium chlorohydroxide that is mixed with by prior art (as USP4, being introduced in 176,090 or USP4,248,739) are diluted to 30～1000mmol Al/ liter, use NH
4OH or NaOH adjust and keep its pH4～6, wear out 2～24 hours down at 50～75 ℃, are cooled to room temperature and place more than 2 hours, make the aluminum crosslinker of high-basicity (OH/Al) thus.
3. back crosslinking reaction:, the microballoon of above-mentioned moulding is added in the linking agent with the feed ratio of 1.0～5.0mmol Al linking agent by every gram clay, uses NH
4OH transfers its pH4～6, carries out crosslinking reaction 0.5～3 hour under 50～75 ℃, filters then, washs, drying, and 650 ℃ of roastings promptly got catalyst prod provided by the invention in 1～3 hour.
This back crosslinking reaction also can be undertaken by three times or four pulp crosslinking methods, that is: by the feed ratio of every gram clay with 1.0～5.0mmol Al linking agent, the moulding microballoon is added to the Al that is dissolved with total amount 1/3～1/4 will joins 20～40 times of agent in the deionized water of microballoon weight, use NH
4OH adjusts and keeps its pH4～6, carries out pulp crosslinked 15 minutes under 50～75 ℃, filters then.So wash again after the repetitive operation 3～4 times, dry, roasting.
Three, dispersion agent method
The characteristics of this method are by adding the organic substance dispersion agent in arbitrary component before shaping of catalyst or the preparation process among above-mentioned two kinds of preparation methods.Specifically, this method is such:
In the arbitrary component or step before the catalyzer spray shaping, add the polyvinyl alcohol or the fluorocarbon surfactant of catalyst weight 0.1～3.0%, and wore out 0.5～24 hour down, and then carry out subsequent step by set program at 20～75 ℃.
One of embodiment is that polyvinyl alcohol with catalyst weight 1～3% joins in the aluminium colloidal sol preferably, 20～75 ℃ aging 0.5～24 hour down, and then with clay, auxiliary activity component and carrier ingredients making beating, spray shaping.
Two of embodiment is that fluorocarbon surfactant with catalyst weight 0.1～0.2% joins in the slurries to be formed that contain each component precursor of catalyzer preferably, mixes spray shaping.
Microballoon after the moulding is aging by foregoing washing, filter, dry, 650 ℃ of roastings promptly got catalyst prod provided by the invention in 1～3 hour.
In above three kinds of preparation methods, what employed raw material swellable clay was meant the various natural or synthetic that comprises rectorite leng and smectite has expansile regular interbed mineral clay or an individual layer mineral clay, be preferably rectorite leng or smectite, preferably rectorite leng.The constitutional features of rectorite leng has detailed description in ZL CN87104718.
Raw material as carrier can be the clay of kaolin group, wherein is preferably halloysite; It also can be one or both the mixture that contains in the inorganic oxide of Si, Al, Zr.
Catalyzer provided by the invention can be done Hydrocarban coversion catalysts, also can flood or exchange last other element and make catalyst action, can also use with other catalyst mix, certainly also can be used as sorbent material or carrier, yet the catalytic cracking that it is specially adapted to heavy oil or mixes residual oil is with voluminous gasoline and diesel oil.
Compared with the prior art, the present invention has following advantage:
1. catalyst prod provided by the invention is made up of and content the best.Wherein the layer clay active ingredient helps pressure fuel; Auxiliary activity component y-type zeolite can be adjusted selectivity of catalyst preferably; Novel friendship stick component is then useful to improving catalyst strength, therefore the catalyzer provided by the invention abrasive wear resistance that compared with prior art has higher heavy oil conversion performance and petrol and diesel oil yield and can reach industrial service requirements.
2. preparation method provided by the invention is reasonable, is easy to industrialization.All eliminate the filter operation step of fine particle clay among three kinds of preparation methods provided by the invention, therefore be easy to industrialization.Especially hand in the stick method aluminium colloidal sol and pseudo-boehmite or the intensification of metal aluminum shot mixed together, when aluminium colloidal sol is by pseudo-boehmite or metallic aluminium modification, the acid that hydrolysis goes out is used for peptization pseudo-boehmite or metallic aluminium again conversely, thereby obtain to play the friendship stick that crosslinked action can play the binding agent effect again, and then the making beating mixing step before crosslinking reaction and the moulding is united two into one, saved the filtration step after the crosslinking reaction among the conventional preparation method, not only simplify flow process, also improved product performance simultaneously.
3. catalyst prod provided by the invention has been widely used.Compare with conventional industrial cracking catalyst, catalyzer of the present invention is pressure fuel more effectively owing to contain layer clay, so it not only can do conventional Hydrocarban coversion catalysts, sorbent material and carrier, and can make heavy oil or mix residue cracking catalyst.On the other hand and since the layer clay active ingredient to the cracking ability of small molecules raw material a little less than, thereby it is easy to keep diesel oil and gasoline, can be as the cracking catalyst of pressure fuel fecund vapour, diesel oil.
Preparation method provided by the invention has been owing to adopted good hydrothermal stability, layer clay component that hydrogen transfer activity is low, thereby also is applicable to preparation rare hydrocarbon of voluminous low-carbon (LC) or high temperature pyrolysis catalyzer.
Following example will give further instruction to the present invention.
Example 1
The catalyzer of the present invention that the explanation of this example hands over the stick method to prepare has high reactivity, strong heavy oil conversion performance, good petrol and diesel oil selectivity and coke selectivity, and qualified abrasive wear resistance and heap ratio are arranged.
With 10.96Kg Al
2O
3Content is aluminium colloidal sol (Zhou village, Shandong catalyst plant) and the 1.65Kg Al of 22.8 heavy %
2O
3Content is that the thin water-aluminum hydroxides (Zhou village, Shandong catalyst plant) of the plans of 30.35 heavy % add water and mix, kept 0.5 hour down at 90～100 ℃, being cooled to 70 ℃ wore out 2.5 hours, be cooled to room temperature, adding the 9.2Kg solid content is 65.65 heavy %, rare earth exchanged the rectorite leng slurries stirred 0.5 hour, adding 1.0Kg (butt) extremely steady y-type zeolite of rare earth (Qilu Petrochemical company catalyst plant) again stirred 0.5 hour, obtaining solid content is the slurries of 35 heavy %, spray shaping is consisted of: 60 heavy % layer post rectorite lengs then, 10 heavy %Y type zeolites, 30 heavy %Al
2O
3The microspherical catalyst of binding agent.
This microspherical catalyst is carried out the washing burin-in process three times, washed 15 minutes down in 60 ℃ with 20 times of water at every turn to example weight.Use for the first time NH
4OH regulates the deionized water of pH to 7～9, is that 2～3 phosphorus content is the H of 0.04 weight % with pH for the second time
3PO
4And NH
4The OH mixing solutions.Use NH for the third time
4OH regulates the deionized water of pH to 5～6.Microballoon after the burin-in process adopts ordinary method filtration, drying, promptly got catalyzer provided by the invention in 2 hours through 650 ℃ of roastings then.
This catalyzer with standard chemical process analyze chemical constitution list in table 1.
The intensity (abrasion index) that BET specific surface that the basal spacing that records with X-optical diffraction, cryogenic nitrogen absorption record and pore volume fluidisation abrasion method record is all listed in table 2.
The catalytic performance of estimating out with heavy oil microreactor the results are shown in table 3.Sample was through 800 ℃, 100% steam-treated 4 hours before estimating.Appreciation condition is as follows: 227～475 ℃ triumph wax oil is a raw material, 520 ℃ of temperature of reaction, and agent-oil ratio 3 is during weight hourly space velocity 16
-1
In order to compare, the cracking catalyst that contains rare earth hydrogen Y zeolite (Zhou village, Shandong catalyst plant) that existing industry is used is also estimated in the lump under the same conditions, and the result lists in table 3 simultaneously.
By table 2 and table 3 as can be seen, catalyzer of the present invention has qualified intensity and heap ratio, compare with industrial rare earth hydrogen Y catalyzer, it not only catalytic activity height but also heavy oil conversion performance to exceed 3.6 units, gasoline and exceed 9 units, diesel oil and exceed 2.8 units, the selectivity of coke also is better than this industrial agent.Table 1
| Main chemical constitution | Na 2O CaO Fe 2O 3 RE 2O 3 Al 2O 3 SiO 2 |
| Content, heavy % | 1．10 2．70 0．47 0．99 51．9 42．4 |
Table 2
| Basal spacing (d001), A | Specific surface, m 2／g | Pore volume, ml/g | Abrasion index | The heap ratio, g/ml |
| 28．0 | 170 | 101 | 202 | 0．75 |
Table 3
Example 2
This example illustrates that cracking catalyst provided by the invention is not only applicable to pressure fuel and is applicable to that heavy feed stock that cracking mixes residual oil is to produce vapour, diesel oil.
Prepare by example 1 described method and to consist of: 60 heavy % layer post rectorite lengs, 10 heavy % rare earth hydrogen y-type zeolites, 30 heavy %Al
2O
3The microspherical catalyst of binding agent.
This microspherical catalyst is carried out the washing burin-in process four times, washed 15 minutes down in 60 ℃ with 20 times of water at every turn to example weight. use NH for the first time
4OH regulates the deionized water of pH to 7～9.With pH5～6, phosphorus content the H of 0.04 heavy % for the second time and for the third time
3PO
4And NH
4The mixing solutions of OH.Use NH the 4th time
4OH regulates the deionized water of pH5～6.Microballoon after the burin-in process after filtration, drying, 650 ℃ of roastings promptly got catalyzer provided by the invention in 2 hours.
The chemical constitution of this catalyzer is listed in table 4.Physical and chemical performance is listed in table 5.List in table 6 through 800 ℃, its cracking performance gained result and appreciation condition of the sample heavy oil micro anti-evaluation of 100% steam-treated after 4 hours to different material.
In order to compare, the cracking catalyst that contains overstable gamma zeolite (Zhou village, Shandong catalyst plant) that existing industry is used is also estimated in the lump under the same conditions, and the result also lists in table 6 simultaneously.
As can be seen from Table 6, no matter catalyzer provided by the invention is the cracking wax oil or mixes residual oil raw material (boiling range is 239～537 ℃) that its activity and light oil (being vapour, diesel oil) yield all are higher than industrial overstable gamma zeolite cracking catalyst under identical appreciation condition; Under same conversion, its light oil yield is also perverse apparently higher than industrial overstable gamma zeolite cracking catalysis.Table 4
Table 5
| Main chemical constitution | Na 2O | CaO | Fe 2O 3 | RE 2O 3 | Al 2O 3 | SiO 2 |
| Content, heavy % | 1.99 | 2.80 | 0.49 | 1.10 | 55.0 | 37.0 |
| Basal spacing (dool), A | Specific surface, m 2／g | Pore volume, ml/g | Abrasion index | The heap ratio, g/ml | ||
| Fresh sample | 800℃4hrs | Fresh sample | 800℃／4hrs | |||
| 27．6 | 153 | 114 | 0．15 | 0．18 | 3．7 | 0．76 |
Table 6
Example 3
| Stock oil | The triumph wax oil | Mix the vacuum gas oil of 34% long residuum | |||
| Catalyzer | Sample of the present invention | Industry USY agent | Sample of the present invention | Industry USY agent | |
| Appreciation condition: temperature of reaction, ℃ agent-oil ratio weight hourly space velocity, the time -1 | 482 4 16 | 482 4 16 | 482 4 16 | 482 4 16 | 482 5 16 |
| Transformation efficiency, heavy % product yield, heavy % gas coke gasoline, diesel heavy oil light oil yield, heavy % | 75.3 10.9 4.0 60.4 17.2 7.5 77.6 | 72.8 15.8 2.5 54.5 16.0 11.2 70.5 | 72.7 12.6 8.8 51.3 18.6 8.7 69.9 | 67.4 14.5 6.7 46.2 17.4 15.2 63.4 | 73.8 16.6 7.7 49.5 15.7 10.5 65.2 |
When the explanation of this example changes aluminium colloidal sol and intends the ratio of thin water-aluminum hydroxide in handing over the stick method, can prepare the catalyst for cracking heavy oil of more highly active voluminous vapour, diesel oil.
According to example 1 described method, aluminium colloidal sol and plan are approached the weight ratio of water-aluminum hydroxide (with Al
2O
3Meter) changes 3: 1 into by 5: 1, be about to 9.9kg Al
2O
3Content is aluminium colloidal sol and the 2.47kgAl of 22.8 heavy %
2O
3Content is that the thin water-aluminum hydroxides of the plans of 30.35 heavy % add water and mix, kept 0.5 hour down at 90～100 ℃, being cooled to 70 ℃ wore out 2.5 hours, be cooled to room temperature, adding 9kg contains the slurries of 6kg butt rare-earth type rectorite leng, stirred 0.5 hour, add 1.0kg (butt) hyperastable Y-type RE zeolite (Shandong company catalyst plant product) stirring again and obtained the slurries that solid content is 35 heavy % in 0.5 hour, spray shaping is consisted of: 60 heavy % layer post rectorite lengs, 10 heavy % extremely steady y-type zeolite of rare earth, 30 heavy %Al then
2O
3The microspherical catalyst of binding agent.
This microspherical catalyst is carried out the once washing burin-in process: use NH
4OH regulate pH to 5～6,20 times to the water of example weight in 60～70 ℃ of following burin-in process 2 hours, filter then, drying, 650 ℃ of roastings promptly got catalyzer provided by the invention in 2 hours.
According to appreciation condition and the evaluation method described in the example 1, estimate with this catalyzer of the little opposition of heavy oil, the results are shown in table 7.Industry overstable gamma zeolite cracking catalyst evaluation result is under the same conditions also listed in table 7 simultaneously.
As can be seen from Table 7, catalyzer of the present invention has the activity higher than industrial ultra-stable Ytype catalyst, strong heavy oil conversion performance and high vapour, diesel yield.Table 7
Example 4
| Transformation efficiency, heavy % | Product yield, heavy % | The light oil total recovery, heavy % | |||||
| Gas | Coke | Gasoline | Diesel oil | Heavy oil | |||
| Sample industry USY of the present invention agent | 81.0 77.2 | 17.1 21.3 | 3.7 2.1 | 60.2 53.8 | 13.5 12.9 | 5.5 9.9 | 73.7 66.7 |
The catalyzer of the present invention that the improved back of this example explanation crosslinking is prepared has high strength, high reactivity and high petrol and diesel oil yield.
With the 9.3kg solid content is that hydrochloric acid and the 7.4kg solid content of the rare-earth type rectorite leng filter cake of 64.5 heavy %, halloysite that the 0.62kg solid content is 81.0 heavy %, 0.49 liter, 37 heavy % is 33.7 heavy % (Al
2O
3Meter) the thin water-aluminum hydroxide of plan adds in the entry successively and mixes, 70 ℃ were worn out 1 hour down, adding 1kg (butt) extremely steady y-type zeolite of rare earth again stirs, obtaining solid content is the slurries of 25 heavy %, spray shaping then, obtain containing 60 heavy % rectorite leng clays, 5 heavy % halloysites, 10 heavy % hyperastable Y-type REs, 25 heavy % through the hydrochloric acid peptization the microballoon intermediate of the thin water alumina binder of plan.
Commercially available aluminium colloidal sol is diluted to 120 mmol Al/ liters, uses NH
4OH regulates and keeps pH5～6, kept 2.5 hours down at 70 ℃, place again more than 2 hours after reducing to room temperature, then by every gram rectorite leng clay with the feed ratio of 4mmol Al with above-mentioned modification aluminum crosslinker mix with the microballoon intermediate, under 70 ℃, the condition of pH5～6, carried out crosslinking reaction 2 hours, after filtration, drying, 650 ℃ of roastings promptly got catalyzer provided by the invention in 2 hours.
The relevant materialization data of this catalyzer are listed in table 8.
Estimate with this catalyzer of the little opposition of heavy oil according to the evaluation method described in the example 1, except that temperature of reaction is 480 ℃, all the other appreciation conditions the results are shown in table 9 with example 1.
The super steady Y cracking catalyst of industry evaluation result is under the same conditions also listed in table 9.
As can be seen from Table 9, catalyzer of the present invention has qualified intensity, heap ratio, is higher than cracking activity, strong heavy oil conversion performance and the high petrol and diesel oil yield of industrial ultra-stable Ytype catalyst.Table 8
| Basal spacing (dool), A | Specific surface, m 2／g | Pore volume, ml/g | Abrasion index | The heap ratio, g/ml | ||
| Fresh sample | 800℃／4hrs | Fresh sample | 800℃／4hrs | |||
| 28．0 | 244 | 145 | 0．198 | 0．174 | 2．3 | 0．81 |
Table 9
Example 5
| Transformation efficiency, heavy % | Product yield, heavy % | The light oil total recovery, heavy % | |||||
| Gas | Coke | Gasoline | Diesel oil | Heavy oil | |||
| Sample industry USY of the present invention agent | 72．0 66．5 | 10．4 11．1 | 3．2 1．5 | 58．5 53．9 | 18．9 20．4 | 9．0 13．1 | 77．4 74．1 |
The catalyzer of the present invention that this example explanation dispersion agent method is prepared has the high reactivity of pressure fuel.Prepare and contain Al according to the described method of handing over stick for preparing of example 1
2O
325 weigh the aluminium colloidal sol of % and contain Al
2O
3The friendship stick of the thin water aluminum oxide of the plan of 5 heavy %.Hand over the rare-earth type rectorite leng and 10 that adds 60 heavy % in the stick to weigh the extremely steady y-type zeolite of rare earth of % to this, stir, add the fluorocarbon surfactant QBS of 0.15 heavy % again
, Shanghai organic fluorine material institute product) and stir spray shaping then.
According to the method described in the example 3 this microspherical catalyst is carried out the once washing burin-in process and obtain catalyzer provided by the invention.
According to appreciation condition and the evaluation method described in the example 1, estimate with this catalyzer of the little opposition of heavy oil, the results are shown in table 10.The evaluation result of industry overstable gamma zeolite cracking catalyst is also listed in table 10.
As can be seen from Table 10, catalyzer of the present invention is compared with industrial ultra-stable Ytype catalyst, and its specific activity latter will exceed 2 units, and heavy oil conversion performance will exceed about 5 units, and the petrol and diesel oil selectivity will exceed 10 units.Table 10
Example 6
| Transformation efficiency, heavy % | Product yield, heavy % | The light oil total recovery, heavy % | |||||
| Gas | Coke | Gasoline | Diesel oil | Heavy oil | |||
| Sample industry USY of the present invention agent | 79．5 77．2 | 15．4 21．3 | 3．3 2．1 | 60．8 53．8 | 15．6 12．9 | 4．9 9．9 | 76．4 66．7 |
The catalyzer of the present invention that this example explanation dispersion agent method is prepared has heavy oil high conversion and the high yield of light oil.
With 68.7kg Al
2O
3Content is that the aluminium colloidal sol of 21.82 heavy % is diluted with water to Al
2O
3Content is 5.44 heavy %, the polyvinyl alcohol water solution 7.5kg that adds 4 heavy %, wore out 3 hours down at 70 ℃, reduce to ambient temperature overnight, adding 11.3kg solid content is that the rare-earth type rectorite leng of 57.8 heavy % stirred 2 hours, add 2.0kg (butt) extremely steady y-type zeolite of rare earth again and stirred 0.5 hour, spray shaping is consisted of: 65 heavy % layer post rectorite lengs, 20 heavy % extremely steady y-type zeolite of rare earth, 15 heavy %Al
2O
3The microspherical catalyst of binding agent.
With this microspherical catalyst NH
4OH regulate pH to 5～6,40 times to the water of example weight in 70 ℃ of following burin-in process 2.5 hours, filter then, drying, 650 ℃ of roastings promptly got catalyzer provided by the invention in 2 hours.
List in table 11. according to appreciation condition and the evaluation method described in the example 1 according to basal spacing, specific surface and pore volume data that the method described in the example 1 records, estimate gained with this catalyzer of the little opposition of heavy oil and the results are shown in table 12.Industry overstable gamma zeolite cracking catalyst evaluation result is under the same conditions also listed in table 12 simultaneously.
As can be seen from Table 12, catalyzer of the present invention is than high 4.6 units of transformation efficiency of industrial ultra-stable Ytype catalyst, and residual unconverted heavy oil lacks 5.5 units, high 3.0 units of light oil yield.Table 11
Table 12
Example 7
| Basal spacing (dool), A | Through the surface, m 2／4hrs | Pore volume, ml/g | ||
| Fresh sample | 800℃／4hrs | Fresh sample | 800℃／4hrs | |
| 27 | 194 | 113 | 0．15 | 0．10 |
| Transformation efficiency, heavy % | Yield, heavy % | |||||
| Gas | Coke | Gasoline | Diesel oil | Heavy oil | ||
| Sample industry USY of the present invention agent | 81.8 77.2 | 22.3 21.3 | 3.6 2.1 | 55.9 53.8 | 13.8 12.9 | 4.4 9.9 |
This example explanation is by method provided by the invention, when changing each component ratio to auxiliary component and being zero, still can obtain the catalyst for cracking heavy oil of highly active voluminous vapour, diesel oil.
To Al
2O
3Content is the metal aluminum shot that adds aluminium colloidal sol weight a thirtieth in the aluminium colloidal sol of 20.7 heavy %, and 94 ℃ were refluxed 6 hours, reduced to ambient temperature overnight, refluxed 6 hours down at 94 ℃ again, obtains the Al/Cl weight ratio and be 1.43, Al
2O
3Content is that the modification aluminium colloidal sol of 24.6 heavy % is handed over stick.
With the 13.2kg solid content be the rare-earth type rectorite leng of 64.5 heavy % and the above-mentioned modification aluminium of 6.09kg colloidal sol add water mixed solid content be 38 heavy % slurries, spray shaping, consisted of: the layer post rectorite leng of 85 heavy % and 15 heavy %Al
2O
3The microspherical catalyst of binding agent.
With this microspherical catalyst NH
4OH regulate pH to 5～6,20 times to the water of example weight in 70 ℃ of following burin-in process 2.5 hours, filter then, drying, 650 ℃ of roastings promptly got catalyzer provided by the invention in 2 hours.
According to appreciation condition and the evaluation method described in the example 1, estimate gained with this catalyzer of the little opposition of heavy oil and the results are shown in table 13.
As can be seen from Table 13, even do not have auxiliary activity component and carrier clay composition, catalyzer provided by the invention still has high heavy oil conversion performance and light oil yield.Table 13
| Transformation efficiency, heavy % | Yield, heavy % | The heavy % of light oil yield | |||||
| Gas | Coke | Gasoline | Diesel oil | Heavy oil | |||
| Sample of the present invention | 75．7 | 13．2 | 6．9 | 55．6 | 17．7 | 6．6 | 73．3 |
Claims (10)
1. laminar column clay microphere cracking catalyst for heavy oil is characterized in that:
(1) it consists of: the chemical ingredients of the layer clay of 20～90 heavy %, 10～40 heavy % is mainly the y-type zeolite of the binding agent of aluminum oxide, 0～40 heavy % and kaolin group's clay of 0～70 heavy %;
(2) layer clay wherein is with being selected from pseudo-boehmite, metallic aluminium, NH
4The aluminium colloidal sol of one of OH, NaOH, polyvinyl alcohol, fluorocarbon surfactant modification or contain Al
13O
4(OH)
24(H
2O)
12 + 7The hydroxy aluminum mixture be interlayer support thing predecessor's aluminium cross-linked swellable clay;
(3) binding agent is wherein formed by its precursor drying roasting, its precursor can be with the aluminium colloidal sol that forms behind direct peptization pseudo-boehmite of acid that is obtained by the aluminium sol-hydrolysis after aluminium colloidal sol and pseudo-boehmite or the metallic aluminium mixing intensification or the metallic aluminium and the mixture of alumina gel, also can be with adding the colloidalmaterial that forms behind the method peptization pseudo-boehmite of mineral acid, can also be aluminium colloidal sol and/or the alumina gel that contains polyvinyl alcohol or fluorocarbon surfactant or silicon-aluminum sol.
2. according to the described catalyzer of claim 1, what it is characterized in that wherein said swellable clay is meant the various natural or synthetic that comprises rectorite leng and smectite has expansile regular interbed mineral clay or an individual layer mineral clay.
3. according to the described catalyzer of claim 1, it is characterized in that wherein said y-type zeolite can make the transition through ion-exchange, also can be that the structure cell that obtains after the disclosed physics of various prior aries and/or chemical means are handled shrinks or the y-type zeolite of non-shrinking modification.
4. claim 1 Preparation of catalysts method is characterized in that this method can be to hand over the stick method, has following three steps:
(1) stick is handed in preparation: with aluminium colloidal sol and thin water-aluminum hydroxide of plan or aluminum oxide, with Al
2O
3Meter mixes by 2: 1～5: 1 weight ratios, adds an amount of water so that the solid content of gained slurries is 15～30 heavy %, keeps 0.1～1.5 hour, 50～70 ℃ aging 1～3 hour postcooling to room temperature through 90～100 ℃; Or aluminium colloidal sol and metallic aluminium mixed by 30: 1 weight ratio, refluxing 6～13 hours at 90～95 ℃, the colloidalmaterial of gained is chilled to room temperature;
(2) making beating spray shaping: will the above-mentioned friendship stick that makes with swellable clay, y-type zeolite and carrier component according to 10～40: 20～90: 0～40: 0～70 weight ratio is mixed and was pulled an oar 1～3 hour, is spray dried to microballoon;
(3) aging washing: thus obtained microsphere is carried out the aging washing of one or many, and at last in 450～650 ℃ of roastings 1～3 hour, wherein once the condition of aging washing is as follows: with 20～40 times of deionized water NH to example weight
4OH transfers its pH5～6, under 60～75 ℃ microballoon is worn out 0.5～3 hour, filters drying then;
Wherein repeatedly the condition of aging washing is as follows, for the first time: with 20～40 times of water NH to example weight
4OH transfers its pH6～9,50～75 ℃ of following washing microballoons 15 minutes, filters; For the second time: with 20～40 times to example weight, phosphorus content is 0.03～0.10% phosphoric acid solution NH
4OH transfers its pH2～6,50～75 ℃ of following washing microballoons 15 minutes, filters; As desire many washings once, then wash conditions is with for the second time; For the last time: with 20～40 times of water NH to example weight
4OH transfers its pH4～6, washs aging microballoon down at least 15 minutes at 50～75 ℃, filters drying.
5. claim 1 Preparation of catalysts method is characterized in that this method can be an improved back crosslinking, and it comprises following three steps:
(1) preparation clay microphere: with the pseudo-boehmite component of swellable clay component, carrier component, usefulness hydrochloric acid peptization, with Al
2O
3Meter, and y-type zeolite is according to 20～90: 0～70: 10～40: 0～40 weight ratio mixing is also made slurries, the spray shaping that solid content is 20～30 heavy %;
(2) preparation modified crosslinking agent: aluminium colloidal sol or polymerization aluminium chlorohydroxide are diluted to 30～1000mmolAl/ liter, use NH
4OH or NaOH adjust and keep its pH4～6, wear out 2～24 hours down at 50～75 ℃, are cooled to room temperature and place more than 2 hours;
(3) back crosslinking reaction:, the microballoon of moulding is added in the linking agent with the feed ratio of 1.0～5.0mmol Al linking agent by every gram clay, uses NH
4OH transfers its pH4～6, carries out crosslinking reaction 0.5～3 hour under 50～75 ℃, filters then, washs, drying, 650 ℃ of roastings 1～3 hour.
6. according to the described preparation method of claim 5, it is characterized in that back crosslinking reaction wherein also can be undertaken by three times or four pulp crosslinking methods, that is: by the feed ratio of every gram clay with 1.0～5.0mmol Al linking agent, 20～40 times that the moulding microballoon are added to the Al linking agent that is dissolved with total amount 1/3～1/4 in the deionized water of microballoon weight, use NH
4OH adjusts also and keeps its pH4～6, carries out pulp crosslinked 15 minutes under 50～75 ℃, filters then, so washs after the repetitive operation 3～4 times, dry, roasting again.
7. according to claim 4 or 5 described preparation methods, it is characterized in that in the arbitrary component or step before the catalyzer spray shaping, can also add the polyvinyl alcohol of catalyst weight 0.1～3.0% or fluorocarbon surfactant as dispersion agent, after under 20～75 ℃ aging 0.5～24 hour, carry out subsequent step by set program again.
8. according to the described preparation method of claim 7, it is characterized in that this method is: the polyvinyl alcohol of catalyst weight 1～3% is joined in the aluminium colloidal sol, 20～75 ℃ aging 0.5～24 hour down, and then with clay, auxiliary activity component and carrier ingredients making beating, spray shaping.
9. according to the described preparation method of claim 7, it is characterized in that this method is: the fluorocarbon surfactant of catalyst weight 0.1～0.2% is joined in the slurries to be formed that contain each component precursor of catalyzer, mix spray shaping.
10. according to claim 4 or 5 described preparation methods, it is characterized in that the clay in the catalyst component is a rectorite leng.
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| CN97116446A CN1060204C (en) | 1997-09-17 | 1997-09-17 | Laminar column clay microphere cracking catalyst for heavy oil and its preparation |
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|---|---|---|---|
| CN97116446A CN1060204C (en) | 1997-09-17 | 1997-09-17 | Laminar column clay microphere cracking catalyst for heavy oil and its preparation |
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| CN1060204C true CN1060204C (en) | 2001-01-03 |
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| CN101797492B (en) * | 2010-04-16 | 2012-04-04 | 北京化工大学 | Method for preparing laminated dihydroxy composite metal hydroxide porous microspheres |
| CN105749957B (en) * | 2014-12-16 | 2018-09-04 | 中国石油天然气股份有限公司 | Composite binder, preparation method and application thereof |
| 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 |
|---|---|---|---|---|
| CN1031489A (en) * | 1987-08-22 | 1989-03-08 | 中国石油化工总公司石油化工科学研究院 | The Preparation of catalysts that contains clay molecular sieve with layer structure |
| CN1043270A (en) * | 1988-12-17 | 1990-06-27 | 中国石油化工总公司石油化工科学研究院 | Has the preparation that improves the tart cross-linked clay |
| CN1071945A (en) * | 1992-12-11 | 1993-05-12 | 黄忠喜 | Stable macropore and high-crystallinity layer clay microspherical catalyst, its preparation method and application |
| US5360775A (en) * | 1991-12-18 | 1994-11-01 | Mitsubishi Material Corporation | Porous clay intercalation compound and its production method |
-
1997
- 1997-09-17 CN CN97116446A patent/CN1060204C/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1031489A (en) * | 1987-08-22 | 1989-03-08 | 中国石油化工总公司石油化工科学研究院 | The Preparation of catalysts that contains clay molecular sieve with layer structure |
| CN1043270A (en) * | 1988-12-17 | 1990-06-27 | 中国石油化工总公司石油化工科学研究院 | Has the preparation that improves the tart cross-linked clay |
| US5360775A (en) * | 1991-12-18 | 1994-11-01 | Mitsubishi Material Corporation | Porous clay intercalation compound and its production method |
| CN1071945A (en) * | 1992-12-11 | 1993-05-12 | 黄忠喜 | Stable macropore and high-crystallinity layer clay microspherical catalyst, its preparation method and application |
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