CN1762598A - Metal catalytic cracking deactivator and its preparation method - Google Patents
Metal catalytic cracking deactivator and its preparation method Download PDFInfo
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- CN1762598A CN1762598A CN 200510030083 CN200510030083A CN1762598A CN 1762598 A CN1762598 A CN 1762598A CN 200510030083 CN200510030083 CN 200510030083 CN 200510030083 A CN200510030083 A CN 200510030083A CN 1762598 A CN1762598 A CN 1762598A
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Abstract
This invention relates to a deactivator which is used for inhibiting the metal pollution of the hydrocarbons catalytic cracking catalyst, in addition to its preparing method, wherein the deactivator is comprises the compound including boron. The deactivator prepared through said method has great deactivating effort on the nickel in the hydrocarbons catalytic cracking catalyst, and the distribution of the product will improve greatly; the productivity of the ideal produce petrol will increase 2,5~4 percent; the productivity of the non ideal product will decreased, wherein the productivity of the hydrogen gas will decrease 20~40%.
Description
Technical field
The present invention relates to a kind of passivator of suppressing the catalyst and cracking of hydrocarbon metallic pollution and preparation method thereof that is used to.
Background technology
In the catalytic cracking of hydrocarbon process, particularly be in the catalytic cracking process of raw material with the mink cell focus, heavy metal that contains in the raw material such as Fe, Ni, V, Ca etc. can constantly be deposited on the surface of catalytic cracking catalyst, cause catalysqt deactivation and selectivity variation, cause hydrogen and coke yield to increase, gasoline and yield of light oil reduce.Metallic pollution at catalytic cracking catalyst, industrial except raw material being carried out the demetalization preliminary treatment, selecting for use the strong catalyst of preventing from heavy metal ability, can also adopt the replacement rate that strengthens catalyst to improve the character of catalyst, and use passivator to suppress the toxic action of the metal pair catalyst in the raw material.Wherein using passivator is cheap and the most simple and effective method, and behind the use passivator, the conversion ratio of feedstock oil and some the key technical indexes are improved widely.
Early stage matal deactivator is some inorganic or organic compounds that contain antimony, as CN 87106236, and US4031002, US 4394324 etc.Modal is dihydroxy phosphordithiic acid antimony, and at normal temperatures, this compounds is a solid, must earlier it be dissolved in the solvent during use, just can be injected on the commercial plant then, and not only operating process is loaded down with trivial details, but also can give out the smell of stimulation.Patent US 4488998, and US 4507389, and it is the matal deactivator and the preparation thereof of carboxylic acid antimony or trihydroxy ethanethio antimony that US 5389233 discloses main component.Under the normal temperature, such passivator is liquid, is dissolved in deep fat, and storage temperature is not very high, is acid, and equipment is had certain corrosivity.Patent CN 99121443.9, and CN 98117512.0, and CN 97116889.x, US4599772, US 4609747 disclose some and water misciblely contained antimony passivator and preparation thereof.Such passivator has the advantage of the convenience used and remove, storage and transportation safety.
Can effectively suppress the toxic action of nickel though contain the passivator of antimony to catalytic cracking catalyst, but also there are some defectives, as antimonial human body is had bigger harm, antimony is attached to the result of use that can reduce CO combustion promoter on the Cracking catalyst when burning.For this reason, non-antimony passivator occurred, patent CN 88102585, and CN 91101411.x, CN 92108912.0 disclose the matal deactivator and the preparation thereof of bismuth-containing, and the blunt nickel effect of bismuth-containing passivator is not as antimony passivator, but toxicity is little than antimony passivator.Patent CN 99121443.9, CN99107788.1, US 4921824 discloses the passivator that contains rare-earth elements of lanthanum, cerium, and reaction conversion ratio and gasoline yield all are improved, hydrogen yield descends, and simultaneously the harmful effect that overcomes vanadium in the catalytic cracking process is also had certain inhibitory action.
Summary of the invention
The objective of the invention is to overcome the shortcoming that existing passivator technology toxicity is big, price is more expensive, provide a kind of nontoxic, preparation process simple, preparation condition relaxes, cheap catalytic cracking metal passivant, and provides the preparation method of this passivator.
The present invention is achieved through the following technical solutions:
The compound that the invention provides a kind of boracic is characterized in that as catalytic cracking metal passivant described catalytic cracking metal passivant is as follows than proportioning by quality:
Hydramine 20～30%
Solvent 10～40%
Boron compound 40～60%
In said components, described boron compound is boric acid, boron oxide, reaches their mixture, is preferably boric acid;
Described hydramine is one or more of aliphatic hydramine, particular methanol amine, monoethanolamine, Propanolamine, diethanol amine and composition thereof;
The optional water of described solvent, alcohol, ester type compound and composition thereof;
When hydramine was diethanol amine, the proportioning of boron compound and diethanol amine was 2.0～4.0 (mass ratioes);
When hydramine was selected carbinolamine, monoethanolamine, Propanolamine for use, the proportioning of boron compound and these hydramine was 1.5～5.0 (mass ratioes).
Further improved technical scheme of the present invention is: the compound that a kind of boracic and phosphorus are provided is characterized in that as catalytic cracking metal passivant described catalytic cracking metal passivant is as follows than proportioning by quality:
Hydramine 20～30%
Solvent 10～40%
Boron compound 40～60%
Phosphorus compound 1～30%
In said components, described boron compound is boric acid, boron oxide and their mixture, is preferably boric acid;
Described hydramine is one or more of aliphatic hydramine, particular methanol amine, monoethanolamine, Propanolamine, diethanol amine and composition thereof;
Described phosphorus compound is phosphorus pentoxide, phosphoric acid, metaphosphoric acid, organic phosphorus compound and their mixture;
The optional water of described solvent, alcohol, ester type compound and composition thereof;
When hydramine was diethanol amine, the proportioning of boron compound and diethanol amine was 2.0～4.0 (mass ratioes);
When hydramine was selected carbinolamine, monoethanolamine, Propanolamine for use, the proportioning of boron compound and these hydramine was 1.5～5.0 (mass ratioes).
In addition, the invention provides the preparation method of above-mentioned matal deactivator:
Described preparation method comprises: hydramine is mixed in proportion with solvent, stir and be warming up to 30～150 ℃, add boron compound, and reacted 0.2～5 hour under 30～150 ℃ of temperature, be prepared into the passivator of boracic after the question response thing complete reaction; Wherein, the mass ratio of each component is:
Hydramine 20～30%
Solvent 10～40%
Boron compound 40～60%.
The further improved method of the present invention is: add phosphorus-containing compound in the passivator of boracic, reacted 0.2～5 hour under 30～150 ℃ of temperature, be prepared into the passivator of boracic and phosphorus, wherein, the mass ratio of each component is:
Hydramine 20～30%
Solvent 10～40%
Boron compound 40～60%
Phosphorus compound 1～30%.
The specific embodiment:
The present invention is further elaborated below by embodiment, but do not limit protection scope of the present invention.
Embodiment 1
Prepare passivator according to method provided by the invention.
With 50 gram deionized waters and 16 gram diethanol amine (commercial reagent, analyze pure) add at the bottom of the garden have reflux condenser in the flask, stir heat temperature raising down, when temperature reaches 70 ℃ of left and right sides, add 35.2 gram boric acid (commercial reagent is analyzed pure), and under this temperature stirring and refluxing 0.5 hour, behind the complete water white transparency of question response product, this moment, the pH value of solution was neutral, promptly got passivating agent products A after the cooling.The density (20 ℃) of measuring product with the described method of GB/T2540-81 is 1.16 gram per centimeters
3The kinematic viscosity (40 ℃) of measuring product with the described method of GB/T265-88 is 9.52 millimeters
2/ second; The condensation point of measuring product with the described method of GB/T510-83 is less than being-10 ℃; Analyze through the X XRF, boron content is 5.8% among the passivator A.
Embodiment 2
Prepare passivator according to method provided by the invention.
With 50 gram deionized waters and 16.5 gram diethanol amine (commercial reagent, analyze pure) add at the bottom of the garden have reflux condenser in the flask, stir heat temperature raising down, when temperature reaches 80 ℃ of left and right sides, add 29.2 gram boric acid (commercial reagent, analyze pure), and under this temperature stirring and refluxing 0.5 hour, behind the complete water white transparency of question response product, add phosphoric acid 3.66 grams, continue to stir 20 minutes, this moment, the pH value of solution was neutral, promptly got passivating agent products B after the cooling.The density (20 ℃) of measuring product with the described method of GB/T2540-81 is 1.18 gram per centimeters
3The kinematic viscosity (40 ℃) of measuring product with the described method of GB/T265-88 is 9.82 millimeters
2/ second; The condensation point of measuring product with the described method of GB/T510-83 is less than being-10 ℃; Analyze through the X XRF, boron content is 5.6% among the passivator B.
Example 3
The passivation effect of matal deactivator provided by the invention is described.
Get the passivator A of example 1 preparation, be impregnated into nickel content according to a certain percentage and be on the LB-1 cracking equilibrium catalyst of 6000ppm (product that Lanzhou Oil Refinery is produced), 120 ℃ of oven dry constant weights, in 537 ℃ of roasts 10 hours, obtain the catalyst that boron content is respectively 2000ppm, 3000ppm, 4000ppm, 5000ppm again.With triumph oil plant decompression two wires oil is raw material, on fixed fluidized bed reaction unit above-mentioned five kinds of catalyst is estimated.Appreciation condition is: catalyst loading amount 60 grams, 490 ℃ of reaction temperatures, reaction pressure are normal pressure, oil ratio 3.35, weight (hourly) space velocity (WHSV) 12 hours
-1, the results are shown in table 1.
Table 1
| Boron content ppm on the catalyst | Conversion ratio w% | Yield of gasoline w% | Diesel yield w% | Coke yield w% | Hydrogen yield w% |
| 0 | 82.15 | 29.05 | 23.50 | 3.52 | 0.717 |
| 2000 | 80.23 | 31.60 | 24.00 | 3.12 | 0.582 |
| 3000 | 79.54 | 32.73 | 23.77 | 3.01 | 0.486 |
| 4000 | 79.78 | 33.24 | 23.27 | 2.94 | 0.485 |
| 5000 | 77.79 | 32.10 | 23.24 | 2.75 | 0.419 |
The result of table 1 shows that the passivator for preparing with method provided by the invention has tangible passivation to the nickel on the catalytic cracking catalyst.Under the same conditions, compare with the catalyst of not handling with the catalyst that passivator was handled through passivator, the distribution of product has obtained tangible improvement, the productive rate of desired product gasoline increases by 2.5～4 percentage points, the productive rate of non-ideal product coke and hydrogen descends, and the productive rate of hydrogen has descended 20～40%.
Example 4
The passivation effect of matal deactivator provided by the invention is described.
Get the passivator B of example 2 preparations, be impregnated into nickel content according to a certain percentage and be on the LB-1 cracking equilibrium catalyst of 6000ppm (product that Lanzhou Oil Refinery is produced), 120 ℃ of oven dry constant weights, in 537 ℃ of roasts 10 hours, obtain the catalyst that boron content is respectively 2000ppm, 3000ppm, 4000ppm, 5000ppm again.With triumph oil plant decompression two wires oil is raw material, on fixed fluidized bed reaction unit above-mentioned five kinds of catalyst is estimated.Appreciation condition is: catalyst loading amount 60 grams, 490 ℃ of reaction temperatures, reaction pressure are normal pressure, oil ratio 3.35, weight (hourly) space velocity (WHSV) 12 hours
-1, the results are shown in table 2.
Table 2
| Boron content ppm on the catalyst | Conversion ratio w% | Yield of gasoline w% | Diesel yield w% | Coke yield w% | Hydrogen yield w% |
| 0 | 82.15 | 29.05 | 23.50 | 3.52 | 0.717 |
| 2000 | 80.10 | 32.72 | 23.70 | 3.00 | 0.550 |
| 3000 | 79.90 | 33.45 | 23.48 | 2.95 | 0.482 |
| 4000 | 79.80 | 33.84 | 23.50 | 2.95 | 0.450 |
| 5000 | 79.77 | 32.67 | 23.10 | 2.80 | 0.430 |
The result of table 2 shows that the passivator for preparing with method provided by the invention has tangible passivation to the nickel on the catalytic cracking catalyst.Under the same conditions, compare with the catalyst of not handling with the catalyst that passivator was handled through passivator, the distribution of product has obtained tangible improvement, the productive rate of desired product gasoline increases by 3.5～5 each percentage point, the productive rate of non-ideal product coke and hydrogen descends, and the productive rate of hydrogen has descended 20～40%.
Claims (6)
1, a kind of catalytic cracking metal passivant is characterized in that, described catalytic cracking metal passivant is as follows than proportioning by quality:
Hydramine 20～30%
Solvent 10～40%
Boron compound 40～60%
In said components, described boron compound is one or more a mixture in boric acid, the boron oxide;
Described hydramine is one or more of aliphatic hydramine;
One or more mixture in the optional water of described solvent, alcohol, the ester type compound.
2, catalytic cracking metal passivant as claimed in claim 1 is characterized in that, described hydramine is one or more a mixture in carbinolamine, monoethanolamine, Propanolamine, the diethanol amine.
3, catalytic cracking metal passivant as claimed in claim 1 is characterized in that, when hydramine was diethanol amine, the mass ratio of boron compound and diethanol amine was 2.0～4.0;
When hydramine was selected carbinolamine, monoethanolamine, Propanolamine for use, the mass ratio of boron compound and these hydramine was 1.5～5.0.
4, catalytic cracking metal passivant as claimed in claim 1 is characterized in that, described catalytic cracking metal passivant is as follows than proportioning by quality:
Hydramine 20～30%
Solvent 10～40%
Boron compound 40～60%
Phosphorus compound 1～30%
Described phosphorus compound is one or more a mixture of phosphorus pentoxide, phosphoric acid, metaphosphoric acid, organic phosphorus compound kind.
5, a kind of preparation method of catalytic cracking metal passivant as claimed in claim 1, it is characterized in that, described preparation method comprises: hydramine is mixed in proportion with solvent, stirring is warming up to 30～150 ℃, add boron compound, and under 30～150 ℃ of temperature, reacted 0.2～5 hour, be prepared into the passivator of boracic after the question response thing complete reaction; Wherein, the mass ratio of each component is:
Hydramine 20～30%
Solvent 10～40%
Boron compound 40～60%.
6, the preparation method of catalytic cracking metal passivant as claimed in claim 5 is characterized in that, adds phosphorus-containing compound in the passivator of boracic, under 30～150 ℃ of temperature, reacted 0.2～5 hour, be prepared into the passivator of boracic and phosphorus, wherein, the mass ratio of each component is:
Hydramine 20～30%
Solvent 10～40%
Boron compound 40～60%
Phosphorus compound 1～30%.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB200510030083XA CN100540141C (en) | 2005-09-28 | 2005-09-28 | Catalytic cracking metal passivant and preparation method thereof |
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| CNB200510030083XA CN100540141C (en) | 2005-09-28 | 2005-09-28 | Catalytic cracking metal passivant and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104066819A (en) * | 2011-11-21 | 2014-09-24 | 巴斯夫公司 | Improved metal passivator/trap for FCC processes |
| CN105829504A (en) * | 2013-12-19 | 2016-08-03 | 巴斯夫公司 | Boron Oxide In Fcc Processes |
| CN108906135A (en) * | 2018-07-24 | 2018-11-30 | 淄博凯美可工贸有限公司 | Double-function catalyzing cracking matal deactivator and preparation method |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101885980B (en) * | 2010-07-26 | 2012-11-21 | 金浦新材料股份有限公司 | Preparation method and application of catalytic cracking metal passivant |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104066819A (en) * | 2011-11-21 | 2014-09-24 | 巴斯夫公司 | Improved metal passivator/trap for FCC processes |
| CN104066819B (en) * | 2011-11-21 | 2016-12-07 | 巴斯夫公司 | Matal deactivator/trapping agent for the improvement of FCC technique |
| CN105829504A (en) * | 2013-12-19 | 2016-08-03 | 巴斯夫公司 | Boron Oxide In Fcc Processes |
| CN108906135A (en) * | 2018-07-24 | 2018-11-30 | 淄博凯美可工贸有限公司 | Double-function catalyzing cracking matal deactivator and preparation method |
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| CN100540141C (en) | 2009-09-16 |
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