阅读说明：本技术 一种双金属钝化剂制备工艺 (Preparation process of bimetal passivator ) 是由 石肖 于 2019-11-21 设计创作，主要内容包括：本发明公开了一种双金属钝化剂制备工艺,属于石油化工技术领域。本发明工艺包括依次进行的三步骤：单锑钝化剂制备、单铈钝化剂制备和复合钝化剂制备的步骤,本发明利用有机酸与有机胺按一定比例进行反应,进而与三氧化二锑、碳酸铈形成螯合物,并形成水溶性钝化剂产品。本发明相对传统钝化剂工艺没有使用双氧水作为原料,从而降低了生产过程的风险性,并杜绝了工人接触双氧水所产生的危害。本发明工艺与现有技术相比较保留三氧化二锑结构,且无需通过双氧水氧化形成五氧化二锑,相比较五氧化二锑,三氧化二锑分子中锑含量更高,当单位质量的氧化锑沉积到催化剂上时,催化剂表面的锑含量更高,挂锑率也更高。(The invention discloses a preparation process of a bimetal passivator, and belongs to the technical field of petrochemical industry. The process comprises the following three steps in sequence: the preparation method comprises the steps of single antimony passivator preparation, single cerium passivator preparation and composite passivator preparation. Compared with the traditional passivating agent process, the invention does not use hydrogen peroxide as a raw material, thereby reducing the risk of the production process and avoiding the harm caused by the contact of workers with hydrogen peroxide. Compared with the prior art, the process provided by the invention retains an antimony trioxide structure, and antimony pentoxide is not required to be formed by oxidizing hydrogen peroxide, compared with antimony pentoxide, the antimony content in antimony trioxide molecules is higher, when antimony oxide of unit mass is deposited on the catalyst, the antimony content on the surface of the catalyst is higher, and the antimony hanging rate is higher.)

1. A preparation process of a bimetal passivator is characterized by comprising the following three steps of: preparing a single antimony passivator, preparing a single cerium passivator and preparing a composite passivator;

preparing a antimony trioxide passivator:

firstly, pumping an organic acid raw material into a kettle, pumping one of ethanolamine, triethanolamine, triethylamine and diethanolamine into a head tank, and dropping while cooling and stirring;

secondly, continuously stirring for a certain time after the dripping is finished, opening a manhole cover and adding antimony trioxide into the kettle;

thirdly, heating to 80-130 ℃ after feeding, keeping the reaction kettle sealed in the heating process, opening a condenser valve and a cooling water valve, condensing and refluxing for 1-4 hours, sampling and observing that a reaction solution is reddish brown and transparent, finishing the reaction, and cooling to below 50 ℃;

fourthly, pumping deionized water into the kettle to obtain a finished antimony deactivator;

preparing a single cerium passivator:

firstly, sequentially pumping one of ethanolamine, triethanolamine, triethylamine or diethanolamine and deionized water into a kettle;

secondly, opening a manhole, and adding the organic acid raw material while cooling;

thirdly, controlling the temperature between 30 and 60 ℃, and slowly adding cerium carbonate;

fourthly, continuously heating to 70-110 ℃, reacting until the temperature is transparent, and then cooling to obtain a finished product of the antimony-free passivator;

preparing a composite passivator:

firstly, mixing the single antimony passivator and the single cerium passivator prepared in the above way according to a certain proportion to obtain the bifunctional catalytic cracking metal passivator.

2. The process for preparing a bimetal passivator as defined in claim 1, wherein: the organic acid raw material is one of lactic acid, oxalic acid, citric acid, tartaric acid or malic acid.

3. The process for preparing a bimetal passivator as claimed in claim 2, wherein: the preferred mass ratio of the organic acid raw material, ethanolamine, triethanolamine, triethylamine, diethanolamine, antimony trioxide and deionized water in the preparation step of the antimony trioxide passivator is 4:2:2: 1.

4. A process for preparing a bimetallic passivator as claimed in claim 3, wherein: in the preparation step of the mono-cerium passivator, the mass ratio of the ethanolamine, the triethanolamine, the triethylamine, the diethanolamine to deionized water, the organic acid raw material and the cerium carbonate is 5:20:10: 8.5.

Technical Field

The invention belongs to the technical field of petrochemical industry, and particularly relates to a preparation process of a bimetallic passivator.

Background

With the continuous development of catalytic cracking (FCC) technology and the driving of benefit factors of residue processing, the residue blending rate of catalytic cracking (FCC) units is continuously increased, and some units have realized full residue feeding. The heavy and poor raw materials also cause many problems affecting the economic operation of the apparatus, and among them, metal contamination, especially heavy metal contamination, is one of the more prominent problems.

Currently, the polluting metals of FCC catalysts have been found to mainly include nickel, vanadium, iron, copper, sodium, calcium, magnesium, potassium, lead, etc., and the most common ones are nickel, vanadium, iron and sodium, among which the influence of nickel and vanadium on the catalyst is the most serious, and in many FCC documents, the polluting metals almost become the names of nickel and vanadium. The contamination and passivation of cracking catalysts by heavy metals such as nickel, vanadium, etc. is a complex physical-chemical process. Nickel mainly promotes dehydrogenation reaction, so that the selectivity of the catalyst is reduced; vanadium mainly destroys the molecular sieve structure of the catalyst, so that the activity of the catalyst is reduced. With the widespread use of molecular sieve catalysts, it was found that nickel and vanadium have no synergistic effect on the poisoning of the catalyst, i.e., vanadium and nickel are independent of the poisoning of the catalyst.

Since the 70 s industrialization, the research and development work of the metal passivator technology has been progressing and become one of the important technologies for catalytic cracking, especially for residual oil catalytic cracking. The metal deactivator is prepared with organic and inorganic compounds of some metals, such as antimony, cerium, tin, etc. and through liquid injection into FCC reaction-regeneration system to deposit on the catalyst, and interacts with the deposited metal to inhibit the contamination of the catalyst. Because the existing metal passivator generally adopts hydrogen peroxide as a raw material to oxidize the antimony trioxide into antimony pentoxide, and then the antimony pentoxide is used as a water-soluble antimony agent. Due to the chemical properties of hydrogen peroxide, safety problems exist in the process of preparing the metal passivator, and workers can be harmed by contacting the hydrogen peroxide.

Disclosure of Invention

Aiming at the technical problems existing in the prior art, the invention aims to provide a preparation process of a bimetal passivator.

Therefore, the invention adopts the following technical scheme: a preparation process of a bimetal passivator is characterized by comprising the following three steps of: preparing a single antimony passivator, preparing a single cerium passivator and preparing a composite passivator;

preparing a antimony trioxide passivator:

firstly, pumping an organic acid raw material into a kettle, pumping one of ethanolamine, triethanolamine, triethylamine and diethanolamine into a head tank, and dropping while cooling and stirring;

secondly, continuously stirring for a certain time after the dripping is finished, opening a manhole cover and adding antimony trioxide into the kettle;

thirdly, heating to 80-130 ℃ after feeding, keeping the reaction kettle closed in the heating process, opening a condenser valve and a cooling water valve, condensing and refluxing, carrying out heat preservation reaction for 1-4 hours, taking samples, observing that the reaction liquid is reddish brown and transparent, finishing the reaction, and cooling to below 50 ℃;

fourthly, pumping deionized water into the kettle to obtain a finished antimony deactivator;

preparing a single cerium passivator:

firstly, sequentially pumping one of ethanolamine, triethanolamine, triethylamine or diethanolamine and deionized water into a kettle;

secondly, opening a manhole, and adding the organic acid raw material while cooling;

thirdly, controlling the temperature between 30 and 60 ℃, and slowly adding cerium carbonate;

fourthly, continuously heating to 70-110 ℃, reacting until the temperature is transparent, and then cooling to obtain a finished product of the antimony-free passivator;

preparing a composite passivator:

firstly, mixing the single antimony passivator and the single cerium passivator prepared in the above way according to a certain proportion to obtain the bifunctional catalytic cracking metal passivator.

In addition to the above technical solutions, the present invention also includes the following technical features.

The organic acid raw material is one of lactic acid, oxalic acid, citric acid, tartaric acid or malic acid.

The preferred mass ratio of the organic acid raw material, ethanolamine, triethanolamine, triethylamine, diethanolamine, antimony trioxide and deionized water in the preparation step of the antimony trioxide passivator is 4:2:2: 1.

In the preparation step of the mono-cerium passivator, the mass ratio of the ethanolamine, the triethanolamine, the triethylamine, the diethanolamine to deionized water, the organic acid raw material and the cerium carbonate is 5:20:10: 8.5.

The invention can achieve the following beneficial effects: 1. the invention does not adopt the raw material of hydrogen peroxide in the preparation process, thereby reducing the risk of the production process and avoiding the harm to workers caused by contacting the hydrogen peroxide. 2. The invention utilizes organic acid, organic amine and antimony trioxide to form chelate, so that a water-soluble product is formed. Compared with the prior art, the antimony content in antimony trioxide molecules is higher. When the antimony oxide of unit mass is deposited on the catalyst, the antimony content on the surface of the catalyst is higher, and the antimony hanging rate is also higher. 3. The bifunctional catalytic cracking metal passivator is flexible to use, and can be flexibly compounded and used by using the single cerium agent and the single antimony agent according to the types and the contents of required effective components and metals contained in oil products.

Detailed Description

Preparing a antimony trioxide passivator:

1. 2000kg of lactic acid (oxalic acid, citric acid, tartaric acid, malic acid) was pumped into a kettle.

2.1000kg of ethanolamine (triethanolamine, triethylamine, diethanolamine) is pumped into a head tank, and the mixture is dropped while cooling and stirring.

3. After the dropwise addition, the mixture was stirred for 5 minutes, and 1000kg of antimony trioxide was added to the kettle by opening the manhole cover.

4. After the feeding, the temperature is raised to 110 ℃, the reaction kettle is kept closed in the temperature raising process, a condenser valve and a cooling water valve are opened, condensation reflux is carried out, the heat preservation reaction is carried out for 2.5 hours, the reaction liquid is reddish brown and transparent after the sampling observation, the reaction is finished, and the temperature is reduced to below 50 ℃.

5. 500kg of deionized water is pumped into the kettle to obtain the finished product of the antimony trioxide.

Preparing a single cerium passivator:

1. 500kg of ethanolamine (triethanolamine, triethylamine, diethanolamine) and 2000kg of deionized water were sequentially pumped into a kettle

2. Opening manhole, cooling while adding 1000kg lactic acid (oxalic acid, citric acid, tartaric acid, malic acid)

3. The temperature was controlled between 50 ℃ and 850kg of cerium carbonate was slowly added. The feeding speed is noticed, a large amount of bubbles are generated in the reaction, and the material is easy to wash.

4. The temperature is increased to 80 ℃, and the reaction is carried out until the reaction is transparent.

5. And cooling to obtain the finished product of the antimony trioxide.

Preparing a composite passivator:

and mixing the single antimony passivator and the single cerium passivator according to a certain proportion to obtain the bifunctional catalytic cracking metal passivator.

The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.