CN101590432B - Modified clay and preparation method thereof - Google Patents
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Abstract
The invention relates to a modified clay and a preparation method thereof. The modified clay is prepared by being roasted at 800-1100 DEG C for 0.3-10h, comprising the following materials by mass percentage: 0.1-3.0 of P, 0.1-4.0 of RE2O3 and 0.1-1.5 of Na2O; the pore volume of the modified clay is 0.1-0.5ML/g, the specific surface is 50-400m<2>/g, and the average grain diameter is 0.5-15[mu]m. The preparation method comprises the following steps: roasting clay at 800-1100 DEG C for 0.3-10h, mixing the roasted clay and deionized water evenly, adding inorganic alkali solution with 0.5-15 mol/L of OH-concentration in the mixture to react at 50-100 DEG C for 0.1-5h and obtaining clay slurry, wherein, the mass ratio of deionized water to clay (counts with dry basis) is 1.5-10, the mass ratio of inorganic alkali solution to clay (counts with dry basis) is 0.5-8, and the inorganic alkali is selected out of one or more of sodium hydroxide, water glass, ammonia and sodium meta-aluminate; filtering the clay slurry, washing the obtained clay slurry by inorganic acid solution at 30-100 DEG C, introducing phosphorus and rare earth in the manner of soaking, then filtering and drying to obtain the modified clay.
Description
Technical field
The present invention relates to a kind of modified clay and preparation method thereof, more specifically is used modified clay of a kind of catalyst and cracking of hydrocarbon that is used for heavy oil transformation and preparation method thereof.
Background technology
Catalytic cracking catalyst is the important oil refining catalyst of a class, and the clay carrier content of preparation catalytic cracking catalyst can reach more than 50%, has brought into play extremely important physics and chemical action.Clay mainly comprises kaolinite family, smectite family, and sepiolite group, wherein kaolinite family consumption accounts for more than 80%.At present, the clay carrier filler of Cracking catalyst great majority are protokaolin, do not have reactivity basically.Along with an urgent demand of heaviness, poor qualityization and catalytic cracking process process residual oils day by day of crude oil in the global range, wish that carrier of cracking partly has the macromolecular reactivity of stronger cracked fuel oil, and improve the preventing from heavy metal ability of catalyst.For this reason, can carry out modification to the used clay carrier of preparation catalyst handles.
USP4843052 relates to a kind of sour modified kaolin, and the kaolin after the modification is (0.8～1.0) Al
2O
3.2SiO
2, specific surface is greater than 150m
2/ g, its preparation method be with the kaolin fine powder 700～910 ℃ of roastings, with acidic materials (example hydrochloric acid) reactions, having made average pore size is the sour modified kaolin of 2～4nm then.This modified kaolin has certain gas oil reactivity, can reduce Cracking catalyst mesolite content.But its hydrothermal stability is relatively poor.
EP358261A1 catalytic cracking catalyst has comprised the modified kaolin composition: kaolin or roasting kaolin and H in its catalyst
3PO
4, H
28O
4, CH
3One of COOH reacted 1～100 hour at 20～110 ℃, had also improved kaolinic reactivity.
The catalytic cracking process of US483691 zeolite containing catalyst and carrier has adopted the kaolin of modification, the method for modification to be in its catalyst, the temperature of roasting kaolin is brought up to more than 1000 ℃, reacts with NaOH again, and having prepared specific surface is 150～350m
2/ g, pore volume are the alkali modification kaolin of 0.3～1.0mL/g.Adopt this modified kaolin as catalyst carrier, can increase reactivity effectively, improve anti-Ni, the V pollutant performance of catalyst.But Zhi Bei modified kaolin is as catalyst carrier in this way, and the coke selectivity of catalyst is relatively poor.
CN1186105A relates to a kind of modified kaoling for cracking hydrocarbons catalyst and manufacture method thereof of containing, and catalyst is formed and comprised: 5～35% particle I, and/or 95～65% existing Cracking catalyst particle II.Wherein particle I is by 0～30% rare earth oxide/alkaline earth oxide that mainly exists with cerium oxide, the sour extracting metakaolin of 10-95%, and/or zeolite/molecular sieve of 0～40%, 0～50% kaolin and 0～15% aluminium chloride colloidal sol are formed.Its sour extracting metakaolin (0.8～1.0) Al
2O
3.2SiO
2, specific surface is greater than 100m
2/ g, there is the relatively poor problem of coke selectivity of catalyst in Zhi Bei modified kaolin as catalyst carrier in this way.
CN1195014A relates to improvement of kaolin, with kaolin 850～920 ℃ of roastings 10 minutes to 5 hours, then at 90～1500 ℃, mol ratio with inorganic monoacid and binary acid is 1.0～5.0, and acid strength is that the mixed acid solution of 0.4～4N is handled the kaolin 4～40 hours after the roasting.The scope that is distributed in 5～20nm is concentrated in kaolinic hole with this method modification, can be used as the particularly carrier component of catalytic cracking catalyst of the hydrocarbon conversion.There is the relatively poor problem of coke selectivity of catalyst in Zhi Bei modified kaolin equally as catalyst carrier in this way.
As can be seen, modified clay of the prior art mostly is high temperature modified or the soda acid modification, adopts element modified clay not occur as yet.Existing method of modifying by 400～1000 ℃ high temperature modified or by acid, the alkali treatment chemical modification all is to improve the effective way of the used kaolin clay reactivity worth of Cracking catalyst.But the subject matter one that existing method of modifying exists is that the silicon sucrose extraction is too high in the kaolin, causes product yield low; The 2nd, the acidity in the modified kaolin is strong excessively, increases considerably coke and select productive rate when improving the catalyst heavy oil transformation; The 3rd, partially modified flow process will be passed through high-temperature roasting, crystallization, process such as ion-exchange, roasting repeatedly, causes long, problem such as product yield is low of modification cycle.
Summary of the invention
The objective of the invention is to overcome deficiencies such as modified clay acidity is strong excessively in the prior art, the modification cycle is long, product yield is low, it is moderate to disclose a kind of acidity, can obviously improve modified clay of the optionally phosphorous and rare earth of catalyst coke and preparation method thereof as the interpolation component of catalytic cracking catalyst.
A kind of modified clay disclosed in this invention, modified clay are through 800～1100 ℃, and the clay after the roasting in 0.3～10 hour in modified clay quality 100%, contains P 0.1～3.0%, RE
2O
30.1～4.0%, Na
2O 0.1～1.5%, modified clay pore volume 0.1～0.5mL/g, specific surface 50～400m
2/ g, average grain diameter 0.5～15 μ m.
Modified clay disclosed in this invention, in modified clay quality 100%, its P content preferred 0.5～2.0%.
Modified clay disclosed in this invention, in modified clay quality 100%, its RE
2O
3Content preferred 0.5～3.0%.
Modified clay disclosed in this invention, preferred 1～10 μ m of its average grain diameter.
The preparation method of modified clay disclosed in this invention comprises: clay was 800～1100 ℃ of roastings 0.3～10 hour; Clay after the roasting and deionized water are mixed, add concentration and be 0.5～15 mole of hydroxide ion/liter inorganic alkali solution, at 50～100 ℃, reacted 0.1～5 hour, obtain clay slurry, wherein, deionized water be 1.5～10 in the clay weight ratio of butt, inorganic alkali solution be 0.5～8 in the clay weight ratio of butt, inorganic base be in NaOH, waterglass, ammoniacal liquor, the sodium metaaluminate one or more; Clay slurry is filtered, wash with inorganic acid solution, introduce phosphorus and rare earth then, filter drying at 30～100 ℃.
The introducing mode of phosphorus and rare earth can adopt the precipitation method, exchange process or infusion process, as long as can reach the content requirement of phosphorus and rare earth in the product.The present invention recommends to adopt the mode of dipping to mirror phosphorus and rare earth.
The concrete preparation process that the present invention recommended is:
(1) average grain diameter be 0.5～15 μ m clay 800～1100 ℃ of roastings 0.3～10 hour, preferred 0.5～7 hour.
Preferred 1～10 μ m of the average grain diameter of clay.
Clay can be one or more in kaolin, galapectite, imvite, sepiolite, diatomite, bentonite, the lamellar clay, preferred kaolin and/or galapectite.
Among the preparation method of modified clay disclosed in this invention, should select average grain diameter for use is the clay of 0.5～15 μ m.This is because adopt the less clay of particle diameter in modifying process, can react more fully with alkaline matter, improves modification efficiency.And clay as the matrix components of catalytic cracking catalyst, can have good dispersive property in catalyst preparation process after modification, improves the catalyst reaction performance.
(2) clay after the roasting and deionized water are mixed, add concentration and be 0.5～15 mole of hydroxide ion/liter inorganic alkali solution, at 50～100 ℃, reacted preferred 0.5～3 hour 0.1～5 hour, obtain clay slurry, wherein, deionized water be 1.5～10 in the clay weight ratio of butt, preferred 3～8, inorganic alkali solution be 0.5～8 in the clay weight ratio of butt, inorganic base be in NaOH, waterglass, ammoniacal liquor, the sodium metaaluminate one or more.
Preferred ammoniacal liquor of inorganic base and/or waterglass.
(3) clay slurry is filtered, at 30～100 ℃, with concentration be 0.1～2.0 moles of hydrogen ion/liter the inorganic acid solution washing, inorganic acid solution and be 3～30 in the clay weight ratio of butt.
Inorganic acid can be one or more in sulfuric acid, hydrochloric acid, the nitric acid.
(4) dipping phosphorus and rare earth: clay after the pickling and deionized water making beating, adding phosphorus compound, earth solution handled 0.5～3 hour in 30～100 ℃ under stirring, this phosphorus compound is inorganic phosphate or solubility inorganic phosphate, in the substance weight ratio, clay is in butt, and phosphorus compound is in the quality of contained P elements, and the P/ clay is 0.001～0.03, preferred 0.005～0.02, rare earth is with RE
2O
3The quality meter, RE
2O
3/ clay is 0.001～0.04, preferred 0.005～0.03.Deionized water and clay weight ratio are 10～20.
Phosphorus compound can be one or more in phosphoric acid, phosphorous acid, ammonium phosphate, ammonium dihydrogen phosphate (ADP), diammonium hydrogen phosphate, aluminum phosphate, sodium dihydrogen phosphate, sodium hydrogen phosphate, the pyrophosphoric acid.
Rare earth can be a mixed chlorinated rare earth, one or more in the mixeding acid rare-earth.
At last, more after filtration, drying, get final product the finished product modified clay.
Modified clay disclosed in this invention, the carrier that can be used as catalytic cracking catalyst uses.
Modified clay disclosed in this invention is moderate as catalyst micro-activity height, the acid strength of the preparing carriers one-tenth of catalytic cracking catalyst.Because the present invention has adopted phosphorus and the composite modified treatment technology of rare earth, has reduced the L acid strength of modified clay, because in cracking reaction, radical reaction is mainly induced in L acid, increase coke and dry gas yied, the L acid that institute's ether is strong is disadvantageous to cracking reaction.And after the modification in the clay pore-size distribution the above hole of 10nm obviously increase, with the Cracking catalyst of modified clay as carrier component preparation, the macromolecular cracking ability of its heavy oil can be significantly improved.Therefore, with the carrier of modified clay provided by the invention as catalytic cracking catalyst, with REUSY as main active component, be mixed into glue with metallic aluminium colloidal sol as binding agent, spray into microballoon, the catalyst of preparation can improve coke selectivity when improving heavy oil cracking ability.
Embodiment
Further demonstrate the present invention below, but the present invention is not limited to these embodiment.
(1) the main analytical method of the present invention's employing:
The assay method that table 1 is main
| Project | Method | Standard No. |
| Na 2O，m％? | Flame spectrometry | Q/SYLS?0568-2002 |
| P，m％? | Phosphorus molybdenum colorimetric method | Q/SYLS?0586-2002 |
| RE 2O 3，m％? | Colorimetric method | Q/SYLS?0580-2002 |
| Specific surface, m 2/g? | The thermal desorption chromatography | Q/SYLS?0600-2002 |
| Pore volume, mL/g | The water droplet method | Q/SYLS?0521-2002 |
| Micro-activity, m% | Miniature fixed bed reaction | Q/SYLS?0589-2002 |
| Reaction selectivity | Fixed fluidized bed reaction | Q/SYLS?0641-2002 |
| Granularity | The laser particle analyzer method | Q/SYLS?0519-2002 |
The acid pyridine adsorption infra-red sepectrometry that adopts of clay is tested, and test test condition on Nicolet 510 type infrared spectrometers: sample is evacuated to 10 under 350 ℃/4h
-3Pa cools to 200 ℃ then, the absorption pyridine, and saturated 5min, and 10
-2Remove the pyridine of physical absorption under the Pa, be recorded in 1300～1800cm
-1IR figure in the scope, desorption temperature is respectively 200 ℃, 350 ℃.In worker R figure, wave number is at 1455cm
-1L acid is represented at the peak at place, represents the acid amount with peak height here.
Table 2 feedstock oil main character
| Project | 30% Xinjiang subtracts slag+70% Xinjiang long distillate |
| Density kgm -3(20℃)? | 901.8? |
| Carbon residue/m% | 3.10? |
| Molecular weight | 390? |
| C/m％? | 86.01? |
| H/m％? | 12.56? |
| N/m％? | 0.24? |
| S/m％? | 0.31? |
| Pb/μg·g -1 | 0.97? |
| Ni/μg·g -1 | 8.14? |
| Fe/μg·g -1 | 20.47? |
| V/μg·g -1 | 0.97? |
| Cu/μg·g -1 | 0.96? |
| Alkane/m% | 61.8? |
| Aromatic hydrocarbons/m% | 34.6? |
| Colloid/m% | 3.6? |
| Fore-running/℃ | 306? |
| 10％/℃? | 339? |
| 30％/℃? | 372? |
| 50％/℃? | 416? |
| 70％/℃? | 460? |
| 90％/℃? | 502? |
(2) use raw material specification in the example of the present invention
1. kaolin: China Kaolin Co., Ltd, igloss 15.1%; Galapectite: the Zhuzhou galapectite, igloss 14.8% is industrial goods
2. NaOH: industrial goods, solid; Waterglass: industrial goods, SiO
2250 grams per liters, Na
2O 81 grams per liters
3. dilute sulfuric acid, 0.3 mol; Watery hydrochloric acid, 0.7 mol
4. ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), phosphorous acid, solid is industrial goods; Phosphoric acid, mass concentration 80%
5. re chloride, industrial goods, the silver Rare Earth Company contains rare earth oxide 250 grams per liters; Rare earth nitrate solution, industrial goods, packet header Zheng Chang metal material Co., Ltd contains rare earth oxide 248 grams per liters.
6.REUSY molecular sieve; Aluminium colloidal sol, salic 23.0 heavy % are industrial certified products, CNPC's Catalyst Factory of Lanzhou Petrochemical Company.
Embodiment 1
600g is restrained kaolin 950 ℃ of roastings 1 hour in Muffle furnace, the cooling back mixes with 1500 ml deionized water, add 10 moles of hydroxide ions/liter sodium hydroxide solution 630 gram, under the stirring, be warming up to 92 ℃, stirring reaction 2 hours, filter then, dilute sulfuric acid washing with 5000 milliliters 75 ℃, with the making beating of 5000 ml deionized water, add phosphoric acid 38 grams, 30 milliliters of re chlorides again, stirred 0.5 hour the modified clay A1 that filter, drying obtains the present invention's preparation down at 60 ℃.
Embodiment 2
600g is restrained galapectite 1050 ℃ of roastings 0.5 hour in Muffle furnace, the cooling back mixes with 2500 ml deionized water, add 5 moles of hydroxide ions/liter sodium hydroxide solution 1600 gram and 1 mole of hydroxide ion/liter waterglass 680 restrain, under the stirring, be warming up to 75 ℃, stirring reaction 3 hours, filter then, watery hydrochloric acid washing with 7500 milliliters 75 ℃, with the making beating of 10000 ml deionized water, add ammonium phosphate 25 grams, 36 milliliters of rare earth nitrate solutions again, stirred 2 hours the modified clay A2 that filter, drying obtains the present invention's preparation down at 40 ℃.
Embodiment 3
600g is restrained kaolin 850 ℃ of roastings 3 hours in Muffle furnace, the cooling back mixes with 3500 ml deionized water, add 14 moles of hydroxide ions/liter sodium hydroxide solution 800 gram and 1 mole of hydroxide ion/liter sodium metaaluminate 400 restrain, under the stirring, be warming up to 120 ℃, stirring reaction 1 hour, filter then, dilute sulfuric acid washing with 10000 milliliters 50 ℃, with the making beating of 7500 ml deionized water, add phosphorous acid 9 grams, 50 milliliters of re chlorides again, stirred 1 hour the modified clay A3 that filter, drying obtains the present invention's preparation down at 80 ℃.
Embodiment 4
600g is restrained galapectite 1050 ℃ of roastings 0.5 hour in Muffle furnace, cooling back and 10 moles of hydroxide ions/liter waterglass 2780 grams and 1 mole of hydroxide ion/liter ammoniacal liquor 1200 grams mix, under the stirring, be warming up to 75 ℃, stirring reaction 3 hours, filter then, watery hydrochloric acid washing with 3000 milliliters 75 ℃, pull an oar with 10000 ml deionized water again, add ammonium dihydrogen phosphate (ADP) 20 and diammonium hydrogen phosphate 5 grams, 18 milliliters of rare earth nitrate solutions stirred 3 hours down at 40 ℃, the modified clay A4 that filter, drying obtains the present invention's preparation.
Embodiment 5
600g is restrained kaolin 950 ℃ of roastings 1 hour in Muffle furnace, and the cooling back mixes with 1500 ml deionized water, adds 1 mole of hydroxide ion/liter ammoniacal liquor 1800 restrain, under the stirring, be warming up to 92 ℃, stirring reaction 2 hours filters then, dilute sulfuric acid washing with 5000 milliliters 75 ℃, with the making beating of 5000 ml deionized water, add phosphoric acid 38 grams, 30 milliliters of re chlorides again, stirred 0.5 hour the modified clay A5 that filter, drying obtains the present invention's preparation down at 60 ℃.
Comparative Examples 1
According to U.S. Pat 4836913 embodiment 4 disclosed method modified kaolins.With kaolin 982 ℃ of roastings 2 hours, getting 500 gram roasting kaolins and 2000 ml deionized water mixes, add 580 gram NaOH, under the stirring, be warming up to 95 ℃, reacted 2 hours, filter then, with 5000 milliliters of 75 ℃ of dilute sulfuric acids washings, with 5000 milliliters of 85 ℃ of deionized waters washings, make contrast modified clay B1 again.
Table 3 is the clay alteration condition that adopts in embodiment 1～4 and the Comparative Examples 1.Table 4 is analytical test results of example 1～4 and Comparative Examples 1.
Table 3 clay alteration condition
The character of table 4 modified kaolin
| Sample and instance number | A1? | A2? | A3? | A4? | A5? | B1? |
| Product weight, gram | 350? | 355? | 365? | 350? | 350? | 298? |
| Yield, % | 70? | 71? | 73? | 70? | 70? | 60? |
| Na 2O，％? | 0.25? | 0.45? | 0.15? | 0.10? | 0.10? | 0.35? |
| P，％? | 2.1? | 1.4? | 0.7? | 2.8? | 2.1? | /? |
?
As seen from Table 4, press the modified clay specific surface of the present invention's preparation at 183～214m
2Between/the g, pore volume is between 0.27～0.32mL/g.Compare with Comparative Examples, because the present invention has optimized the modified technique condition, the yield of modified product has improved 10%.
As seen from Table 4, the modified clay of the present invention's preparation has higher acid amount (200 ℃ of desorption temperatures), because the present invention has adopted phosphorus and the composite modified treatment technology of rare earth, has reduced the L acid strength of modified kaolin, L acid strength retention rate is descended 6～9 percentage points.Because in cracking reaction, radical reaction is mainly induced in L acid, increase coke and dry gas yied, the L acid that institute's ether is strong is disadvantageous to cracking reaction.In addition, as seen from Table 2, the modified clay A1 of the present invention's preparation～A5 comparison improves 6-10 unit than the micro-activity of sample.Analysis-by-synthesis estimates to adopt the Cracking catalyst of the modified clay of the present invention's preparation as carrier component, when increasing the macromolecular cracking ability of heavy oil, can improve coke and dry gas selectivity.
Embodiment 6
This example illustrates the reactivity worth of the catalytic cracking catalyst that unmodified clay is made as carrier component.
With unmodified kaolin as carrier, with the REUSY molecular sieve is active component, is binding agent with metallic aluminium colloidal sol, and according to carrier: molecular sieve: binding agent (in aluminium oxide) is that 50: 35: 15 butt weight ratio is mixed into glue, spray into microballoon, obtain catalyst sample C1.
Embodiment 7
The reactivity worth of the catalytic cracking catalyst that the clay that this example explanation utilizes the inventive method modification is made as carrier component.
With modified kaolin A1 as carrier, with the REUSY molecular sieve is active component, is binding agent with metallic aluminium colloidal sol, and according to carrier: molecular sieve: binding agent (in aluminium oxide) is that 50: 35: 15 butt weight ratio is mixed into glue, spray into microballoon, obtain catalyst sample C2.
Embodiment 8
The reactivity worth of the catalytic cracking catalyst that the modified kaolin that this example explanation utilizes the preparation of U.S. Pat P4836913 disclosed method is made as carrier component.
With comparative example B1 as carrier, with the REUSY molecular sieve is active component, is binding agent with metallic aluminium colloidal sol, and according to carrier: molecular sieve: binding agent (in aluminium oxide) is that 50: 35: 15 butt weight ratio is mixed into glue, spray into microballoon, obtain catalyst sample C3.
The reactivity worth of evaluate catalysts C1, C2, C3 on the small fixed flowing bed reactor.Experiment condition: 150 gram catalyst under 800 ℃, 1000% steam aging 10 hours, reaction raw materials are that Xinjiang 30% is mixed slag and mixed and urge material, 500 ℃ of reaction temperatures, oil ratio 5.0, weight space velocity 16h
-1Evaluation result sees Table 5.
The reactivity worth of table 5 modified clay carried catalyst
| Matrix type | Unmodified kaolin | Modified clay A1 of the present invention | Contrast modified clay B1 |
| Catalyst | C1? | C2? | C3? |
| Dry gas, % | 1.9? | 2.1? | 2.3? |
| Rich gas, % | 21.9? | 23.5? | 22.8? |
| Gasoline, % | 49.5? | 49.6? | 49.0? |
| Diesel oil, % | 14.3? | 14.1? | 13.8? |
| Heavy oil, % | 7.5? | 5.5? | 6.7? |
| Coke, % | 4.5? | 4.7? | 5.0? |
| Conversion ratio, % | 77.8? | 79.8? | 79.1? |
| Total liquid is received % | 85.7? | 87.2? | 85.6? |
| Coke selectivity * | 0.0578? | 0.0589? | 0.0632? |
* be defined as: coke yield/conversion ratio
As seen from Table 5, compare with the catalyst C1 that adopts unmodified kaolin as carrier, adopt the catalyst C2 of the clay of modification of the present invention as carrier, under identical reaction condition, conversion ratio improves 2 percentage points, the heavy oil productive rate reduces by 2 percentage points, and total liquid is received and increased by 1.5 percentage points, and heavy oil conversion performance is greatly improved; Simultaneously, compare with the catalyst C3 that adopts the control methods modified clay as carrier, the heavy oil productive rate of C2 reduces by 1.2 units, and coke yield is hanged down 0.3 percentage point, 1.6 units of total liquid receipts raising, coke selectivity reduction by 0.0043, in extremely strong heavy oil conversion performance, have lower coke yield, shown outstanding coke selectivity, show that the big molecule of heavy oil has obtained effective conversion.Why modified clay of the present invention shows excellent residual oil cracking performance, just be that the present invention compares with existing patented technology, optimized the clay alteration condition well, and phosphorus and rare earth composite modification technology have been adopted, reduce acid strength effectively, thereby improved the cracking reaction selectivity of catalyst.
Claims (20)
1. modified clay, modified clay is through 800～1100 ℃, the clay after the roasting in 0.3～10 hour is characterized in that containing P 0.1～3.0%, RE in modified clay quality 100%
2O
30.1～4.0%, Na
2O0.1～1.5%, modified clay pore volume 0.1～0.5mL/g, specific surface 50～400m
2/ g, average grain diameter 0.5～15 μ m.
2. modified clay according to claim 1 is characterized in that modified clay quality 100%, contains P 0.5～2.0%.
3. modified clay according to claim 1 is characterized in that modified clay quality 100%, contains RE
2O
30.5～3.0%.
4. modified clay according to claim 1 is characterized in that average grain diameter 1～10 μ m.
5. the preparation method of modified clay according to claim 1, it is characterized in that this method comprises: clay was 800～1100 ℃ of roastings 0.3～10 hour; Clay after the roasting and deionized water are mixed, add concentration and be 0.5～15 mole of hydroxide ion/liter inorganic alkali solution, at 50～100 ℃, reacted 0.1～5 hour, obtain clay slurry, wherein, deionized water be 1.5～10 in the clay weight ratio of butt, inorganic alkali solution be 0.5～8 in the clay weight ratio of butt, inorganic base be in NaOH, waterglass, ammoniacal liquor, the sodium metaaluminate one or more; Clay slurry is filtered, wash with inorganic acid solution, introduce phosphorus and rare earth in the mode of dipping then, filter drying at 30～100 ℃.
6. the preparation method of modified clay according to claim 5, the average grain diameter that it is characterized in that clay is 0.5～15 μ m.
7. the preparation method of modified clay according to claim 5, the average grain diameter that it is characterized in that clay is 1～10 μ m.
8. the preparation method of modified clay according to claim 5 is characterized in that clay was 800～1100 ℃ of roastings 0.5～7 hour.
9. the preparation method of modified clay according to claim 5 is characterized in that adding inorganic alkali solution, reacts 0.5～3 hour.
10. the preparation method of modified clay according to claim 5 is characterized in that deionized water and clay weight ratio in butt are 3～8.
11. the preparation method of modified clay according to claim 5, it is characterized in that inorganic acid solution concentration be 0.1～2.0 moles of hydrogen ion/liter, inorganic acid solution be 3～30 in the clay weight ratio of butt.
12. the preparation method of modified clay according to claim 5, it is characterized in that the mode of flooding introduces the actual conditions of phosphorus and rare earth and be: clay after the pickling and deionized water making beating, add phosphorus compound, in 30～100 ℃ of processing 0.5～3 hour, this phosphorus compound was inorganic phosphate or solubility inorganic phosphate to earth solution, in the substance weight ratio under stirring, clay is in butt, phosphorus compound is in the quality of contained P elements, and the P/ clay is 0.001～0.03, and rare earth is with RE
2O
3The quality meter, RE
2O
3/ clay is 0.001～0.04, and deionized water/clay is 10～20.
13. the preparation method of modified clay according to claim 12 is characterized in that the P/ clay is 0.005～0.02.
14. the preparation method of modified clay according to claim 12 is characterized in that RE
2O
3/ clay is 0.005～0.03.
15. the preparation method of modified clay according to claim 5 is characterized in that inorganic base is ammoniacal liquor and/or waterglass.
16. the preparation method of modified clay according to claim 5 is characterized in that clay is one or more in kaolin, galapectite, imvite, sepiolite, diatomite, the bentonite.
17. the preparation method of modified clay according to claim 5 is characterized in that clay is kaolin and/or galapectite.
18. the preparation method of modified clay according to claim 5 is characterized in that inorganic acid is one or more in sulfuric acid, hydrochloric acid, the nitric acid.
19. the preparation method of modified clay according to claim 5 is characterized in that one or more the form that P adopt to add in phosphoric acid, phosphorous acid, ammonium phosphate, ammonium dihydrogen phosphate (ADP), diammonium hydrogen phosphate, aluminum phosphate, sodium dihydrogen phosphate, sodium hydrogen phosphate, the pyrophosphoric acid introduces.
20. the preparation method of modified clay according to claim 5 is characterized in that rare earth adopts mixed chlorinated rare earth, one or more in the mixeding acid rare-earth.
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|---|---|---|---|---|
| CN105295451A (en) * | 2015-11-30 | 2016-02-03 | 成都乐氏化工工程有限公司 | Preparation method for nanometer aluminium oxide composite |
| CN109020476B (en) * | 2018-08-30 | 2021-09-14 | 湖北大学 | Modified composite clay and preparation method thereof |
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| CN115555011A (en) * | 2022-08-24 | 2023-01-03 | 碳中能源科技(北京)有限公司 | Auxiliary agent for improving heavy metal pollution resistance of FCC (fluid catalytic cracking) catalyst |
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