CN1057556C - Process for modifying kaolin - Google Patents
Process for modifying kaolin Download PDFInfo
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- CN1057556C CN1057556C CN 97103802 CN97103802A CN1057556C CN 1057556 C CN1057556 C CN 1057556C CN 97103802 CN97103802 CN 97103802 CN 97103802 A CN97103802 A CN 97103802A CN 1057556 C CN1057556 C CN 1057556C
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Abstract
The present invention relates to a method for modifying kaolin, which comprises the following steps: roasting kaolin at the temperature of 850 to 920 DEG C for 10 minutes to 5 hours, and then treating the roasted kaolin for 4 to 40 hours at the temperature of 90 to 150 DEG C with a mixed acid solution of which the mole ratio of inorganic monobasic acid to binary acid is from 1.0 to 5.0 and the concentration is from 0.4 to 4N. Pores of the kaolin modified by using the method are densely dispersed within the range of 50 to 200 angstroms, and the pores can be used as the constituent of a hydrocarbon conversion catalyst, particularly a catalytic cracking catalyst.
Description
The method of modifying that the invention relates to clay is more specifically said so about improvement of kaolin.
Clay, kaolin particularly, because of its acquisition and cheap easily, become hydrocarbon conversion catalyst, a kind of component of often using of FCC catalyzer particularly, its effect generally is the carrier as catalyzer, but its splitting action also can not be ignored the existing a lot of reports of the method for modifying of prior art medium clay soil.
GB2,120,571 disclose a kind of catalyst composition that contains acid-treated metakaolin, described composition is obtained by following method: heat 0.25 hour or more at 700～910 ℃ kaolin, obtain metakaolin, react with enough be selected from hydrochloric acid, nitric acid, their salt or the acid and the described metakaolin of their mixtures then, make aluminum oxide and the acid-respons of 2～25 moles of % in the described metakaolin.US4,843,052 discloses a kind of preparation method of similar metakaolin, this method is included in 700～910 ℃ and heats kaolin more than 1 minute, obtain a kind of active metakaolin, and should the activity metakaolin be selected from by hydrochloric acid, nitric acid, the acid-respons that their salt or their mixture are formed, the consumption of described acid is that every mole of alukalin is less than 1.5 moles.The metakaolin that obtains with the aforesaid method modified kaolin active higher, but because its aperture is less, mean pore size only is 20～40 dusts, pore volume is concentrated in the hole that is distributed in less than aperture 50 dusts, this small-bore metakaolin is not suitable for being used for the pressure fuel macromole, promptly not high enough to the macromolecular lytic activity of heavy oil, and the heavy trend of crude oil change is obvious day by day in the world wide, and its component as the pressure fuel catalyzer can not be met the demands.
EP0,358,261A1 discloses a kind of fluid cracking catalyst composition, said composition contains the clay of 5～50 heavy % crystal aluminosilicates, 0～65 heavy %, as kaolin, 0～50 heavy % active matrix and 5～80 heavy % are with acid-treated kaolin or metakaolin, acid-treated kaolin of described usefulness or metakaolin obtain with the following method: kaolin is mixed making beating with a kind of acid in being selected from sulfuric acid, phosphoric acid or acetic acid, and in 25～110 ℃, at barometric point or be higher than and heated under the barometric point 1～100 hour, washing, preferably dry.Adopt the kaolin or the metakaolin aperture of this method preparation bigger, the catalytic cracking catalyst of making can improve the yield of gasoline, has reduced carbon deposit, but because of its aperture bigger, its specific surface and pore volume are smaller, thereby itself is also not high enough to the macromolecular cracking activity of heavy oil.
The objective of the invention is to overcome the kaolin that obtains with prior art or metakaolin to the not high shortcoming of heavy oil macromole cracking ability, a kind of new higher improvement of kaolin to heavy oil macromole cracking activity that has is provided.
Method provided by the invention comprise with the kaolin high-temperature roasting then with acid-respons, filter, use the deionized water wash product, the product after the dry washing, its key is, described acid refers to the mixing acid of inorganic monobasic and diprotic acid, the mol ratio of monoprotic acid and diprotic acid is 1.0～5.0 in the mixing acid, and acid strength is 0.4～4.0N, and the consumption of acid solution requirement at least can flood described kaolin solid, the kaolin after the roasting and the temperature of acid-respons are 90～150 ℃, and the time is 4～40 hours; The temperature of described high-temperature roasting is 850～920 ℃, roasting time 10 minutes to 5 hours.
According to method provided by the invention, described monoprotic acid is selected from one or more in the inorganic monoprotic acid, example hydrochloric acid, nitric acid, hydrofluoric acid, Hydrogen bromide, perchloric acid etc., wherein preferred hydrochloric acid or nitric acid; Described diprotic acid is selected from one or more in the inorganic diprotic acid, wherein preferably sulfuric acid.Preferred 0.5～the 4.0N of the concentration of described acid solution, the mol ratio of monoprotic acid and diprotic acid preferred 2.5～5.0 in the mix acid liquor.2～10 times of the preferred kaolin weight of described acid solution consumption.
Handy acid treatment, filtration, washing, the dry product of crossing also can pass through calcination process, this roasting process can carry out under 500～650 ℃, roasting time 0.5～6 hour.Kaolin through method modification provided by the invention after roasting or can directly be used as hydrocarbon conversion catalyst without roasting, as the component of catalytic cracking catalyst, also can be again through other processing, after steam-treated, as the component of hydrocarbon conversion catalyst.
Method provided by the invention can be prepared the modified kaolin of pore distribution concentration between 50～200 dusts, this modified kaolin with compare with the kaolin of art methods modification, have higher to the macromolecular cracking activity of heavy oil, and improved selectivity to vapour, diesel oil, for example, the modified kaolin of the present invention's preparation is through 800 ℃, 100% steam-treated 4 hours, with the industrial trade mark is that the superstable gamma-type industry equilibrium catalyst of ZCM-7 mixes by 3: 7 weight ratio, 482 ℃ of temperature of reaction, agent-oil ratio 5, air speed 16 hours
-1Condition under, be the catalytic cracking catalyst of 227～475 ℃ wax oil as boiling range, the transformation efficiency of wax oil can reach 68.9～70.2 heavy %, vapour, diesel oil account for 53～53.6 and 18.0～19.2 heavy % respectively in the product, and under same reaction conditions, using ZCM-7 to make catalyzer, the wax oil transformation efficiency has only 62.0 heavy %, ZCM-7 mixes the back and has only 65 heavy % as catalyzer wax oil transformation efficiency with original soil, ZCM-7 with use US4,843,052 and EP0,358,261A
1When the kaolin of described method modification mixed as catalyzer by same ratio, the wax oil transformation efficiency also had only 66.8～68.5 heavy %, and vapour, diesel oil only account for 51.2～51.8 heavy % and 17.4～17.5 heavy % in the product.
The following examples will the present invention will be further described.
Example 1
By method modified kaolin provided by the invention.
Select kaolin (Suzhou kaolin company product) 920 ℃ of roastings 1 hour in 500 gram Suzhou machines, take by weighing kaolin 60.0 grams after the roasting and 180 milliliters and contain 20.0 milliliter of 37% hydrochloric acid (chemical pure, Beijing Inst. of Chemical Reagent produces) and 3.4 milliliter of 98% vitriol oil (chemical pure, Beijing Inst. of Chemical Reagent's product) mixed acid solution mixes, 100 ℃ of reactions 26 hours, filter, with deionized water wash to there not being acid group, dry, 550 ℃ of roastings 4 hours, get sample A, preparation condition is listed in the table 1, and the physico-chemical property of sample A is listed in the table 2.Wherein specific surface, pore volume and pore distribution adopt cryogenic nitrogen to inhale BET method mensuration.
Comparative Examples 1
Press US4,843,052 disclosed method modified kaolins.
Select kaolin (with example 1) 910 ℃ of roastings 1 hour in 500 gram Suzhou machines, get metakaolin, take by weighing metakaolin 60.0 grams and 180 milliliters of hydrochloric acid solns mixing that contain 31.2 milliliter 37% hydrochloric acid, handled 26 hours at 100 ℃, get comparative sample A ', preparation condition is listed in the table 1, and the physico-chemical property of sample A ' is listed in the table 2.
Example 2
By method modified kaolin provided by the invention.
The preparation method is kaolinic maturing temperature with example 1, and hydrochloric acid and vitriolic ratio are different with the temperature and time of acid-respons in roasting time, the mixing acid, prepare sample B, and preparation condition is listed in the table 1, and the physico-chemical property of sample B is listed in the table 2.
Comparative Examples 2
Press EP0,358,261A
1Described method modified kaolin.
The preparation method is with example 2, be used acid be 180 milliliters of sulphuric acid solns that contain 3.5 milliliter of 98% vitriol oil, prepare comparative sample B ', preparation condition is listed in the table 1, the physico-chemical property of sample B ' is listed in the table 2.
Comparative Examples 3
Press US4,843,052 disclosed method modified kaolins.
Select kaolin 910 ℃ of roastings 1 hour in the Suzhou machine, kaolin after the roasting 60.0 grams are mixed with 180 milliliters of mixing solutionss that contain 2.3 milliliter of 65% nitric acid and 7.0 milliliter of 37% hydrochloric acid, under the condition identical, react with example 2, the physico-chemical property of ", preparation condition and comparative sample B " is respectively in table 1 and the table 2 to prepare comparative sample B.
Example 3～4
By method modified kaolin provided by the invention.
The preparation method is with example 1, be kaolinic maturing temperature, roasting time, hydrochloric acid and vitriolic ratio in the mixing acid, the kaolin after the roasting is different with the temperature and time of acid-respons, prepare sample C and D, the physico-chemical property of preparation condition and C and D is respectively in table 1 and the table 2.
Example 5
By method modified kaolin provided by the invention.
The preparation method is with example 1, be used mixed acid solution be nitric acid and vitriolic mixed acid solution, nitric acid is different with the vitriolic mol ratio in the mixed acid solution, the asynchronism(-nization) of metakaolin and acid-respons, prepare sample E, the physico-chemical property of preparation condition and sample E is respectively in table 1 and the table 2.
From the result of table 2 as can be seen, be distributed in the scope of 50～200 dusts by method provided by the invention than the concentrated area to the hole that kaolin carries out the product that modification obtains, and kaolin is carried out modification with art methods, the pore distribution of the product that obtains or the concentrated scope that is distributed in less than 50 dusts, or concentrate the scope that is distributed in greater than 200 dusts; With method provided by the invention kaolin is carried out specific surface, the pore volume of the product that modification obtains and uses US4, it is suitable that 843,052 disclosed methods are carried out the product that modification obtains to kaolin, and apparently higher than using EP0,358, the described method of 261A1 is carried out the product that modification obtains to kaolin.
Table 1
| Example number | 1 | Comparative Examples 1 | 2 | Comparative Examples 2 | Comparative Examples 3 | 3 | 4 | 5 | ||
| Kaolinic roasting | Maturing temperature, ℃ | 920 | 910 | 920 | 910 | 910 | 880 | 900 | 920 | |
| Roasting time, hour | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 4.0 | 0.2 | 1.0 | ||
| Kaolin and sour reaction after the roasting | Kaolin consumption after the roasting | 60.0 | 60.0 | 60.0 | 60.0 | 60.0 | 60.0 | 60.0 | 60.0 | |
| Acid and acid solution consumption, milliliter | 37% hydrochloric acid | 20.0 | 31.2 | 7.0 | - | 7.0 | 20.0 | 34.2 | - | |
| 65% nitric acid | - | - | - | - | 2.3 | - | - | 15.0 | ||
| 98% sulfuric acid | 3.4 | - | 1.5 | 3.5 | - | 2.6 | 7.4 | 4.3 | ||
| The acid solution total amount | 180.0 | 180.0 | 180.0 | 180.0 | 180.0 | 180.0 | 180.0 | 180.0 | ||
| The equivalent concentration of acid | 2.02 | 2.08 | 0.77 | 0.72 | 0.65 | 1.87 | 3.80 | 2.08 | ||
| The mol ratio of monoprotic acid and diprotic acid | 3.4 | - | 27 | - | - | 4.5 | 2.7 | 2.7 | ||
| Temperature of reaction, ℃ | 100 | 100 | 120 | 120 | 120 | 90 | 145 | 100 | ||
| Reaction times, hour | 26.0 | 26.0 | 8 | 8 | 8 | 35 | 6 | 20 | ||
| The roasting of the product after the acid treatment | Maturing temperature, ℃ | 550 | 550 | 550 | 550 | 550 | 550 | 550 | 550 | |
| Roasting time, hour | 4 | 4 | 4 | 4 | 4 | 4 | 4 | 4 | ||
Table 2
| Example number | 1 | Comparative Examples 1 | 2 | Comparative Examples 2 | Comparative Examples 3 | 3 | 4 | 5 |
| Sample number into spectrum | A | A′ | B | B′ | B″ | C | D | E |
| Specific surface, rice 2/ gram | 209 | 189 | 105 | 42 | 135 | 171 | 133 | 102 |
| Pore volume, milliliter/gram | 0.27 | 0.17 | 0.16 | 0.14 | 0.16 | 0.18 | 0.16 | 0.18 |
| Pore volume distribution, %＜50 dusts, 50～200 dusts＞200 dusts | 37.7 52.6 9.7 | 83.0 16.1 0.9 | 42.3 34.2 23.5 | 6.4 12.5 81.1 | 64.0 17.0 19.0 | 49.7 42.0 8.3 | 46.9 41.6 11.5 | 29.7 31.1 39.2 |
Below example and Comparative Examples explanation with method provided by the invention the catalytic activity that kaolin carries out the product that modification obtains is better than prior art.
Example 6～7
Will be with the kaolin A of method modification provided by the invention and B at 800 ℃, with 100% steam aging after 4 hours, respectively with industrial equilibrium catalyst ZCM-7 (the super-stable Y molecular sieves catalyzer of Zhou village Catalyst Production, contain the 35%REUSY molecular sieve, with aluminium colloidal sol is binding agent, and its chemical constitution is Al
2O
351.2 heavy %, RE
2O
30.56 heavy %, Na
2O 0.4 heavy %, SiO
247.8 heavy %) mix by 3: 7 weight ratios, be that 227～475 ℃ wax oil is a raw material with boiling range, on heavy oil microreactor, carry out activity rating, reaction conditions is: 482 ℃ of temperature of reaction, liquid volume air speed 16 hours
-1, the agent oil volume is than 5.Evaluation result is listed in the table 3.Product adopts gas chromatographic analysis in the table.
Comparative Examples 4～7
The Suzhou machine is selected the kaolin original soil, the modified kaolin A ' of Comparative Examples 1 and Comparative Examples 2 preparations and B ' are respectively at 800 ℃, with 100% steam aging after 4 hours, mix by 3: 7 weight ratio with industrial equilibrium catalyst ZCM-7 respectively, with three kinds of samples making and ZCM-7 poiser this as catalyzer, under the condition identical with example 6～7, carry out activity rating with same stock oil respectively, evaluation result is listed in the table 3.
From the result of table 3 as can be seen (1) with method provided by the invention kaolin is carried out product that modification obtains through 800 ℃, 100% steam aging is after 4 hours, with ZCM-7 by 3: 7 the mixed sample of weight ratio when the catalytic cracking wax oil, the wax oil transformation efficiency can reach 68.9～70.2 heavy %, and under the same conditions, use ZCM-7 industry poiser, the wax oil transformation efficiency has only 62.0 heavy %, ZCM-7 is when making catalyzer after original soil through steam-treated mixes, and transformation efficiency has only 65 heavy %, ZCM-7 with press US4,843,052 and EP0,358,261A
1When making catalyzer after the modified kaolin of disclosed method preparation mixes by same ratio, the wax oil transformation efficiency also has only 66.8～68.5 heavy %, and this illustrates that the kaolinic cracking activity of method modification provided by the invention is higher than the kaolin of art methods modification.From table 2, also can find out in the products distribution, when making catalyzer after mixing with the kaolin of method provided by the invention and ZCM-7, gasoline, the yield of diesel oil all is higher than with the kaolin of the art methods modification vapour when making catalyzer after ZCM-7 mixes, diesel yield, and the content of heavy oil obviously reduces in carbon deposit and the product, this illustrates that the kaolin of method modification provided by the invention compares with the kaolin of art methods modification, improved the macromolecular cracking ability of heavy oil, improved vapour simultaneously, the selectivity of diesel oil, method provided by the invention is better than prior art.
Table 3
| Example number | 6 | Comparative Examples 4 | 7 | Comparative Examples 5 | Comparative Examples 6 | Comparative Examples 7 * |
| Used modified kaolin | A | A′ | B | B′ | Original soil | Do not have |
| Transformation efficiency, heavy % | 70.2 | 68.5 | 68.9 | 66.8 | 65.0 | 62.0 |
| Product distributes, heavy % natural gas liquid diesel oil coke heavy oil | 14.0 53.6 18.0 2.6 11.8 | 13.3 51.8 17.4 3.4 14.1 | 11.2 53.0 19.2 2.7 13.9 | 11.8 51.2 17.5 2.9 16.6 | 10.5 52.5 17.9 2.0 17.1 |
*Catalyzer is the ZCM-7 poiser
Claims (5)
1. improvement of kaolin, comprise the kaolin high-temperature roasting, then with kaolin after this roasting and acid-respons, filter, use the deionized water wash product, product after the dry washing, it is characterized in that described acid refers to the mixing acid of inorganic monoprotic acid and diprotic acid, the mol ratio of monoprotic acid and diprotic acid is 1.0～5.0 in the mixing acid, acid strength is 0.4～4N, the consumption of acid is wanted to flood described kaolin solid at least, and the temperature of kaolin and acid-respons is 90～150 ℃ after the roasting, and the time is 4～40 hours, the temperature of described kaolinic high-temperature roasting is 850～920 ℃, roasting time 10 minutes to 5 hours.
2. according to the described method of claim 1, it is characterized in that described monoprotic acid refers to hydrochloric acid or nitric acid, described diprotic acid refers to sulfuric acid.
3. according to claim 1 or 2 described methods, it is characterized in that described acid strength is 0.5～4.0N.
4. according to claim 1 or 2 described methods, it is characterized in that the mol ratio of monoprotic acid and diprotic acid is 2.5～5.0 in the described mixing acid.
5. according to claim 1 or 2 described methods, the consumption that it is characterized in that described acid is 2～10 times of kaolin weight after the roasting.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97103802 CN1057556C (en) | 1997-03-31 | 1997-03-31 | Process for modifying kaolin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97103802 CN1057556C (en) | 1997-03-31 | 1997-03-31 | Process for modifying kaolin |
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| Publication Number | Publication Date |
|---|---|
| CN1195014A CN1195014A (en) | 1998-10-07 |
| CN1057556C true CN1057556C (en) | 2000-10-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 97103802 Expired - Lifetime CN1057556C (en) | 1997-03-31 | 1997-03-31 | Process for modifying kaolin |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101941714B (en) * | 2009-07-09 | 2012-06-27 | 中国石油化工股份有限公司 | Method for synthesizing molecular sieve by modified kaolin |
| CN104556081B (en) * | 2013-10-28 | 2016-05-04 | 中国石油化工股份有限公司 | A kind of modified kaolin and its preparation method and application |
| CN103897667B (en) * | 2014-03-25 | 2017-01-18 | 中南大学 | Solar heat storage material taking kaolin as supporting basal body and preparation method of solar heat storage material |
| CN105983414B (en) * | 2015-01-28 | 2019-01-18 | 中国石油天然气股份有限公司 | Method for preparing active matrix, catalyst containing active matrix and preparation method thereof |
| CN105251492B (en) * | 2015-10-09 | 2018-07-31 | 张家港中科景盛材料科技有限公司 | A kind of clay modified method for preparing Ni base catalyst |
| CN108097227A (en) * | 2016-11-25 | 2018-06-01 | 中国石油天然气股份有限公司 | Preparation method of mesoporous alumina/clay composite material |
| CN108097285A (en) * | 2016-11-25 | 2018-06-01 | 中国石油天然气股份有限公司 | Preparation method of catalytic cracking catalyst containing mesoporous alumina/clay composite material |
| CN106800298A (en) * | 2016-12-29 | 2017-06-06 | 高州市兆翔新材料有限公司 | A kind of modified kaolin |
-
1997
- 1997-03-31 CN CN 97103802 patent/CN1057556C/en not_active Expired - Lifetime
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|---|---|
| CN1195014A (en) | 1998-10-07 |
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