CN107971040B - Preparation method of catalytic cracking metal passivator and metal passivator prepared by same - Google Patents
Preparation method of catalytic cracking metal passivator and metal passivator prepared by same Download PDFInfo
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- CN107971040B CN107971040B CN201610938210.4A CN201610938210A CN107971040B CN 107971040 B CN107971040 B CN 107971040B CN 201610938210 A CN201610938210 A CN 201610938210A CN 107971040 B CN107971040 B CN 107971040B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J33/00—Protection of catalysts, e.g. by coating
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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- Oil, Petroleum & Natural Gas (AREA)
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Abstract
The invention discloses a preparation method of a catalytic cracking metal passivator and a metal passivator prepared by the method, wherein the method comprises the following steps: a. mixing antimony trioxide, hydroxycarboxylic acid, a boron-containing compound, a bismuth-containing compound, a pH regulator and water, and reacting at the temperature of 20-90 ℃ for 30-60 minutes to obtain a first product; b. and (b) mixing an oxidant with the first product obtained in the step (a), and reacting for 1-2 hours in a closed container at the temperature of 100-150 ℃ to obtain the catalytic cracking metal passivator. The preparation method of the catalytic cracking metal passivator provided by the invention has the advantages of simple preparation process, short reaction time, low cost, reduced energy consumption and remarkable economic benefit. When used in catalytic cracking reaction, the catalytic cracking metal passivator prepared by the method shows good function of passivating nickel and vanadium, can obviously improve the yield of light oil, and reduces the proportion of coke and dry gas in the product.
Description
Technical Field
The invention relates to a preparation method of a catalytic cracking metal passivator and the catalytic cracking metal passivator prepared by the method.
Background
In the catalytic cracking process of heavy oil, heavy metal elements (such as Ni, Fe, V, Cu, etc.) in the raw oil are continuously deposited on the surface of the catalyst, which causes pollution of the catalyst. With the increasing of the deposition amount, the activity and the selectivity of the catalyst are adversely affected, the yield of gasoline and diesel oil is reduced, and the yield of hydrogen and coke is increased. The addition of metal deactivator in the catalytic cracking raw oil is the most economic and effective method for inhibiting the pollution of heavy metal to the catalytic cracking catalyst. Inorganic antimony salt is used as the metal passivator in the early stage, and organic antimony compounds are mostly used as the passivator at present, so that obvious passivation effect is achieved. At present, the metal passivators used in China can be roughly divided into two types, one is an antimony compound dissolved in an organic solvent; the other is an aqueous solution of an antimony compound.
Oil-soluble antimony compounds were used in a large number of early applications. For example, the antimony dithiophosphate dihydroxy reported in Chinese patent CN87106236 and US4694324 needs to be dissolved in an organic solvent before being used, so that the antimony dithiophosphate dihydroxy is strong in pungent smell. The water-soluble antimony passivator is a main type currently applied, and has the advantages of convenience in conveying, good stability, no pungent smell, low toxicity and the like. Chinese patent CN1245198A reports a preparation method of a Sb-containing passivator, and the effect is single. Chinese patents CN104028312A and CN104162455A report that a rare earth element-containing Sb-based passivator can have a bimetallic passivation effect, but the preparation process is complex. The existing preparation process of the double-metal passivator is generally to prepare two single-metal element passivators respectively and then compound the two single-metal element passivators through a solvent, the metal content of the two metal passivators needs to be adjusted, the process is complicated, and the produced metal passivator is high in toxicity and poor in stability.
Disclosure of Invention
The invention aims to provide a preparation method of a catalytic cracking metal passivator and the catalytic cracking metal passivator prepared by the method, so as to solve the problems of complex process, time and energy consumption and poor product stability of the traditional preparation method.
In order to achieve the above object, a first aspect of the present invention: a preparation method of a catalytic cracking metal passivator is provided, which comprises the following steps: a. mixing antimony trioxide, hydroxycarboxylic acid, a boron-containing compound, a bismuth-containing compound, a pH regulator and water, and reacting at the temperature of 20-90 ℃ for 30-60 minutes to obtain a first product, wherein the mass ratio of the antimony trioxide to the hydroxycarboxylic acid to the boron-containing compound to the bismuth-containing compound to the pH regulator to the water is 1: (2-4): (0.5-1.2): (0.4-2): (0.6-1.2): (2-10); b. mixing an oxidant with the first product obtained in the step a, and reacting for 1-2 hours in a closed container at the temperature of 100-150 ℃ to obtain the catalytic cracking metal passivator, wherein the mass ratio of the oxidant to the antimony trioxide is (0.4-1.1): 1.
preferably, the boron-containing compound in step a is boric acid and/or diboron trioxide.
Preferably, the bismuth-containing compound in step a is at least one selected from the group consisting of bismuth oxide, bismuth hydroxide and bismuth nitrate.
Preferably, the pH adjusting agent in step a is at least one selected from the group consisting of ethanolamine, diethanolamine, triethanolamine, aqueous ammonia, sodium dihydrogen phosphate and disodium hydrogen phosphate.
Preferably, the hydroxycarboxylic acid in step a is at least one selected from the group consisting of tartaric acid, citric acid, lactic acid, malic acid and salicylic acid.
Preferably, the reaction described in step a is carried out under stirring conditions.
Preferably, the oxidant in step b is at least one selected from hydrogen peroxide, sodium peroxide, potassium peroxide and benzoyl peroxide.
Preferably, the pH value of the catalytic cracking metal passivator obtained in the step b is 6-8.
Second aspect of the invention: also provided is a catalytic cracking metal deactivator produced by the process of the first aspect of the invention.
Through the technical scheme, the preparation method of the catalytic cracking metal passivator provided by the invention has the advantages of simple preparation process, short reaction time, low cost, reduced energy consumption and remarkable economic benefit. When used in catalytic cracking reaction, the catalytic cracking metal passivator prepared by the method shows good function of passivating nickel and vanadium, can obviously improve the yield of light oil, and reduces the proportion of coke and dry gas in the product. In addition, the catalytic cracking metal passivator provided by the invention has good water solubility, can be mutually dissolved with water in any proportion, is simple and convenient to use, has strong stability, is not easy to generate a flocculation deposition phenomenon, and has a longer storage period.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
In the first aspect of the present invention: a preparation method of a catalytic cracking metal passivator is provided, which comprises the following steps: a. mixing antimony trioxide, hydroxycarboxylic acid, a boron-containing compound, a bismuth-containing compound, a pH regulator and water, and reacting at the temperature of 20-90 ℃ for 30-60 minutes to obtain a first product, wherein the mass ratio of the antimony trioxide to the hydroxycarboxylic acid to the boron-containing compound to the bismuth-containing compound to the pH regulator to the water is 1: (2-4): (0.5-1.2): (0.4-2): (0.6-1.2): (2-10); b. mixing an oxidant with the first product obtained in the step a, and reacting for 1-2 hours in a closed container at the temperature of 100-150 ℃ to obtain the catalytic cracking metal passivator, wherein the mass ratio of the oxidant to the antimony trioxide is (0.4-1.1): 1. it should be noted that, because the catalytic cracking metal passivator prepared by the method of the present invention is generally used in the form of an aqueous solution after being dissolved in water, the amount of water added in the method for preparing the catalytic cracking metal passivator provided by the present invention is not particularly limited, so as to facilitate the operation, for example, the amount of water added may be controlled such that the mass ratio of antimony trioxide to water is 1: (2-10). The method provided by the first aspect of the invention has simple preparation process, can prepare the catalytic cracking metal passivator with good nickel and vanadium passivation function in shorter reaction time, does not need additional pressurization in the reaction, and can reduce energy consumption and have obvious economic benefit. The catalytic cracking metal passivator prepared by reacting at a specific raw material proportion is clear and transparent, has good water solubility, can be mutually dissolved with water at any proportion, has strong stability, is not easy to generate flocculation deposition phenomenon, and has longer storage period.
According to the first aspect of the invention, the formula of the catalytic cracking metal passivator adopts a boron-containing compound and a bismuth-containing compound with nickel passivation performance to replace part of antimony trioxide, so that the product has environmental protection performance. Preferably, the boron-containing compound may be boric acid and/or diboron trioxide. The bismuth-containing compound may be at least one selected from the group consisting of bismuth oxide, bismuth hydroxide and bismuth nitrate.
According to the first aspect of the invention, in order to obtain a clear and transparent catalytic cracking metal deactivator product, a pH regulator is added in the preparation process to regulate the pH of the reaction system, wherein the pH regulator can be an organic base or an inorganic base with weak alkalinity, and the organic base is preferably an alcohol amine compound, and is further preferably at least one selected from ethanolamine, diethanolamine and triethanolamine; the inorganic base is preferably at least one selected from the group consisting of ammonia water, sodium dihydrogen phosphate and disodium hydrogen phosphate. When the pH additive is ammonia water, the concentration of the ammonia water is preferably 10 to 30% by mass.
According to the first aspect of the invention, the hydroxycarboxylic acid can further enhance the water solubility of the catalytic cracking metal deactivator product, making the deactivator system more stable. The hydroxycarboxylic acid refers to an organic compound containing a hydroxyl group and a carboxyl group in a molecule, and may include one or more hydroxyl groups, one or more carboxyl groups, preferably having 2 to 10 carbon atoms, 1 to 4 hydroxyl groups, and 1 to 4 carboxyl groups, and more preferably at least one selected from the group consisting of tartaric acid, citric acid, lactic acid, malic acid, and salicylic acid.
According to the first aspect of the present invention, in order to mix the antimony trioxide, the hydroxycarboxylic acid, the boron-containing compound, the bismuth-containing compound, the pH adjusting agent and the water in step a uniformly to the maximum extent, a mixing method well known to those skilled in the art may be adopted, and preferably, the reaction in step a may be performed under stirring.
According to the first aspect of the present invention, antimony trioxide can be oxidized into antimony pentoxide having a nickel-passivation property by adding an oxidizing agent, which may be at least one selected from the group consisting of hydrogen peroxide, sodium peroxide, potassium peroxide and benzoyl peroxide, preferably 20 to 30 mass% hydrogen peroxide.
According to a first aspect of the invention, the catalytic cracking metal deactivator product produced by the process provided by the invention is a clear and transparent solution having a pH of between 6 and 8, preferably between 7 and 8.
Second aspect of the invention: also provided is a catalytic cracking metal deactivator produced by the process of the first aspect of the invention.
The invention will be further illustrated by the following examples, but is not to be construed as being limited thereto.
The starting materials used in the examples are all chemically pure reagents, unless otherwise specified.
Example 1
Adding 1.8kg of diethanolamine, 6kg of tartaric acid, 3kg of antimony trioxide, 1.2kg of bismuth oxide, 1.5kg of boric acid and 30kg of deionized water into a reaction kettle, stirring for 30 minutes at room temperature, dropwise adding 2kg of 30 mass% hydrogen peroxide, sealing the reaction kettle after adding, heating to 100 ℃ for reaction for 1 hour, cooling and discharging from the kettle to obtain the catalytic cracking metal passivator, wherein the catalytic cracking metal passivator is clear and transparent, and the pH value is 7.1.
Example 2
Adding 2.4kg of ethanolamine, 8kg of citric acid, 2kg of antimony trioxide, 4kg of bismuth hydroxide, 2.4kg of boric acid and 4kg of deionized water into a reaction kettle, heating to 90 ℃, stirring for 30 minutes, dropwise adding 2.2kg of benzoyl peroxide, sealing the reaction kettle after the addition is finished, heating to 150 ℃ for reaction for 1.5 hours, cooling, and taking out of the kettle to obtain the catalytic cracking metal passivator, wherein the catalytic cracking metal passivator is clear and transparent, and the pH value is 8.0.
Example 3
Adding 1.2kg of triethanolamine, 3kg of lactic acid, 1.2kg of antimony trioxide, 1.6kg of bismuth nitrate, 0.8kg of boron trioxide and 7kg of deionized water into a reaction kettle, stirring for 60 minutes at 50 ℃, dropwise adding 2kg of 30 mass% hydrogen peroxide, sealing the reaction kettle after adding, heating to 120 ℃ for reaction for 1 hour, and then cooling out of the kettle to obtain the catalytic cracking metal passivator, wherein the product is clear and transparent, and the pH value is 7.5.
Test example 1
The performance of the examples 1-3 was tested by a light oil micro-reaction test using instruments developed and manufactured by the institute of petrochemical science and technology in China, under the following test conditions: the temperature is 500 ℃, the weight ratio of the agent to the oil is 3, and the oil inlet amount is 1.388 g. The used raw oil is wax oil VGO, the relative molecular mass is 368, and the density at 20 ℃ is 0.91g/cm3Ni content 5.38ppm, V content 1.65 ppm. The compositional analysis of the microreaction was determined using the method of ASTM D7964.
The catalyst used in the test was a catalytic cracking balance (rare earth type fully synthetic zeolite molecular sieve catalyst with a Ni content of 2000ppm and a V content of 600ppm) supplied by Yanshan refinery.
The passivators prepared in examples 1-3 were diluted with the required amount of deionized water, impregnated with the catalyst balance, dried at 150 ℃ for 1h and then baked at 700 ℃ for 3h to prepare test balances 1-3 having Sb contents of 1000, 3000 and 3000ppm, B contents of 100, 700 and 700ppm, and Bi contents of 400, 5000 and 1900ppm, respectively.
The conversion, dry gas selectivity and coke selectivity were calculated according to the following formulas. The test results are shown in Table 1.
Conversion (%) - (dry gas + liquefied gas + gasoline + coke) yield/feed rate × 100%
Dry gas selectivity (%) -. dry gas yield/conversion × 100%
Coke selectivity (%) -. coke yield/conversion × 100%
Test comparative example
The difference from the test examples is that the comparative balancing agent used in the test comparative example was prepared using a commercial brand of Sb-based passivating agent. The test results are shown in Table 1.
TABLE 1
As can be seen from Table 1, when the catalytic cracking metal passivator prepared by the invention is used in a catalytic cracking reaction, the selectivity of dry gas and coke can be obviously reduced, good nickel and vanadium passivation effect is shown, in addition, the yield of light oil can be obviously improved, and the proportion of the dry gas, the hydrogen, the heavy oil and the coke in the product can be reduced.
Claims (8)
1. A method for preparing a catalytic cracking metal deactivator, which comprises:
a. mixing antimony trioxide, hydroxycarboxylic acid, a boron-containing compound, a bismuth-containing compound, a pH regulator and water, and reacting at the temperature of 20-90 ℃ for 30-60 minutes to obtain a first product, wherein the mass ratio of the antimony trioxide to the hydroxycarboxylic acid to the boron-containing compound to the bismuth-containing compound to the pH regulator to the water is 1: (2-4): (0.5-1.2): (0.4-2): (0.6-1.2): (2-10);
b. mixing an oxidant with the first product obtained in the step a, and reacting for 1-2 hours in a closed container at the temperature of 100-150 ℃ to obtain the catalytic cracking metal passivator, wherein the mass ratio of the oxidant to the antimony trioxide is (0.4-1.1): 1;
the pH regulator in the step a is at least one selected from ethanolamine, diethanolamine, triethanolamine, ammonia water, sodium dihydrogen phosphate and disodium hydrogen phosphate.
2. The method of claim 1 wherein the boron-containing compound of step a is boric acid and/or boron trioxide.
3. The method according to claim 1, wherein the bismuth-containing compound in step a is at least one selected from the group consisting of bismuth oxide, bismuth hydroxide and bismuth nitrate.
4. The method according to claim 1, wherein the hydroxycarboxylic acid in step a is at least one selected from the group consisting of tartaric acid, citric acid, lactic acid, malic acid and salicylic acid.
5. The process of claim 1, wherein the reaction in step a is carried out under stirring conditions.
6. The method according to claim 1, wherein the oxidant in step b is at least one selected from hydrogen peroxide, sodium peroxide, potassium peroxide and benzoyl peroxide.
7. The process of claim 1, wherein the catalytic cracking metal deactivator obtained in step b has a pH value of 6-8.
8. A catalytic cracking metal deactivator prepared by the process as claimed in any one of claims 1 to 7.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4595771A (en) * | 1984-11-16 | 1986-06-17 | Atlantic Richfield Company | Water-soluble antimony compounds and their preparation |
| CN102974399A (en) * | 2012-12-11 | 2013-03-20 | 江苏汉光实业股份有限公司 | Preparation method of catalytic cracking metal deactivator |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4595771A (en) * | 1984-11-16 | 1986-06-17 | Atlantic Richfield Company | Water-soluble antimony compounds and their preparation |
| CN102974399A (en) * | 2012-12-11 | 2013-03-20 | 江苏汉光实业股份有限公司 | Preparation method of catalytic cracking metal deactivator |
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