WO2017120798A1

WO2017120798A1 - Oil slurry precipitating agent and method of using same

Info

Publication number: WO2017120798A1
Application number: PCT/CN2016/070802
Authority: WO
Inventors: 熊靓; 严斌; 叶世春; 刘影
Original assignee: 深圳市广昌达实业有限公司; 深圳市广昌达石油添加剂有限公司
Priority date: 2016-01-13
Filing date: 2016-01-13
Publication date: 2017-07-20
Also published as: CN107849465A

Abstract

Provided is an oil slurry precipitating agent, comprising, by weight percent, 10-50% of a poly(meth)acrylate resin, 5-30% of an alkyl quaternary ammonium salt, 5-20% of an alkyl or alkoxy phenolic resin and 25-80% of a solvent. The precipitating agent does not contain environmentally-harmful elements, such as sulfur, halogens, heavy metals, and the like. Moreover, the precipitating agent can be used in small amounts, offers high precipitation efficiency, and can decrease an ash content in an oil slurry to 50 ppm or less, facilitating subsequent processing and utilization of the oil slurry.

Description

Oil slurry settling agent and using method thereof

Technical field

The invention belongs to the field of petroleum additives, and more particularly to a settling agent for removing catalyst powder in a catalytic cracking slurry.

Background technique

Catalytic cracking oil slurry (FCC slurry) is the heaviest part of crude oil, which is rich in colloid, asphaltene and various fused-ring hydrocarbons. It is mainly used as a blending component of heavy fuel oil, and can be further processed. Production of needle coke, asphalt modifier, carbon black and rubber processing aids. However, FCC slurries typically contain from about 0.2 to about 0.6 weight percent of catalyst powder which greatly affects the subsequent use of the FCC slurry. For example, as a fuel oil blending component, the catalyst solid powder may cause the surface area of the furnace to be severely ash, resulting in a decrease in thermal efficiency; the ash content of the carbon black raw material is required to be 500 ppm or less, the superior grade is 200 ppm or less; and the ash content as the hydrogenation raw material is required to be 500 ppm or less. . Therefore, measures must be taken to remove the solid catalyst powder in the FCC slurry.

The method for removing the catalyst powder in the FCC slurry mainly includes a filtration method, a centrifugal separation method, an electrostatic separation method, a natural sedimentation method, an auxiliary sedimentation method, and the like. The filter device has small filter pores, and the filter pores are easy to be clogged, requiring frequent washing, and the operation is complicated; the centrifugal separation method has good effect, but is not suitable for industrial mass production; the separation effect of the electrostatic separation device is unstable, especially after using for a period of time. Natural precipitation method is to make the solid catalyst particles settle naturally by gravity. The method is simple and low in cost, but it takes a long time and the efficiency is too low, and the separation effect is difficult to reach the standard; the auxiliary sedimentation method is based on natural sedimentation, by adding sedimentation. The agent accelerates the settling speed to accelerate the removal of the solid catalyst particles of the FCC slurry. The advantages of the additive sedimentation method are obvious, including the low cost of the additives used, the investment in the equipment required for the process is small, and easy to implement. Most importantly, the method is to purify and modify the FCC slurry. The effect is very good, it can meet the quality requirements of most deep processing and utilization of oil slurry, and the economic benefit is very high. The scientific research workers of various countries have de-solidification technology for the auxiliary sedimentation method. Active research and development has been carried out. USP 4,407,707 discloses a process for the separation of solid particles by washing with a sulfonic acid or a sulfonate, but the process is relatively complicated. CN01113133.0 adopts a method of adding a surfactant-based settling agent to the slurry, maintaining the temperature of the slurry at 50-120 ° C, and sedimenting for 12-60 h, and the removal rate of the catalyst particles in the slurry can reach 70-90%, but the method The required settling time is longer. In addition, most of the slurry settlers currently contain elements such as sulfur and halogen, which are likely to cause environmental pollution. Therefore, the development of a simple, efficient and environmentally friendly slurry settling agent is an urgent and arduous task in the field of research and development of settlers.

Summary of the invention

SUMMARY OF THE INVENTION The object of the present invention is to overcome the deficiencies of the prior art and to provide a highly efficient environmentally friendly settling agent for removing catalyst solid powder from FCC slurry.

The specific scheme of the invention is as follows:

A highly effective environmentally friendly slurry settling agent comprising the following parts by mass: 10-50% poly(meth)acrylic resin, 5-30% alkyl quaternary ammonium salt, 5-20% alkoxy (oxy) group Phenolic resin and 25 to 80% solvent. Preferably, the following components are included: 25 to 35% of a poly(meth)acrylic resin, 15 to 25% of an alkyl quaternary ammonium salt, 10 to 20% of an alkoxyphenol resin, and 35 to 50 % solvent.

Further, the polyacrylic resin is one of polyacrylic acid, polymethacrylic acid or a mixture thereof.

Further, the alkyl quaternary ammonium salt has the formula R ₄ NX, wherein R is the same or different C 1 -C 18 hydrocarbon group, and X is a C 1 -C 4 carboxyl group.

Further, the alkoxyphenol-based phenol resin is one of an ethoxy novolac resin, a propoxy phenol resin or a C4 to C9 alkyl phenol resin.

Further, the solvent is one or a mixture of ethylene glycol, glycerin or pentaerythritol.

The above components are mixed and stirred at 60 ° C for 0.5 to 2 hours to obtain the finished slurry slurry of the present invention. The slurry settling agent of the invention is suitable for FCC slurry removal catalyst solid powder, and the recommended sedimentation temperature is 80-100 ° C, preferably 90 ° C. The recommended addition amount is 500 to 2000 ppm, preferably 800 ppm, and the recommended settling time is 8 to 20 h, preferably 12 h.

Mechanism of action of main components: Poly(meth)acrylic resin is a commonly used flocculant. It is an anionic precipitant. Its function is to destroy and compress the electric double layer, reduce and eliminate the anti-particle phase, and make the catalyst particles flocculate and sink. The alkyl quaternary ammonium salt R ₄ N ⁺ X ^- is a positive ion settling agent with a demulsification effect, which can destroy and compress the electric double layer, reduce and eliminate the anti-particle phase, adsorb the catalyst solid powder, and make it flocculate as soon as possible. . The above two different characteristics of the settling agent have a synergistic effect to enhance the sedimentation effect. The alkoxyphenol-based phenolic resin is a non-ionic type of precipitant which has a strong adsorption effect, which can rapidly agglomerate the solid catalyst particles and accelerate their sedimentation.

The invention has the following advantages: 1) small addition amount, simple operation and good sedimentation effect; 2) no toxicity, no sulfur, phosphorus, heavy metal and the like, and no pollution to the environment.

Specific embodiment

The invention will be further described below in conjunction with specific embodiments. However, the technical content described in this embodiment is illustrative and not limiting, and the scope of the present invention should not be limited thereto.

The raw material catalytic cracking slurry is produced by a company of Sinopec. The main physical and chemical properties are shown in Table 1.

Table 1

Example 1: (Settling agent compounding)

Each of the mass parts of Table 1, polyacrylic resin, alkyl quaternary ammonium salt, and alkoxy phenolic resin was added to the solvent glycerin, and mixed at 60 ° C for 1 hour to prepare different types of settlers.

Table 2

Note: The balance is solvent.

Example 2 (Performance test of compounding settler)

Take 200g of the slurry shown in Table 1, add 800ppm of the settling agent and the commercially available settling agent AH-C80, stir at 90 °C for 0.5 hours, settle at this temperature, take the upper layer of clarified oil slurry according to GB/T508 The ash was measured and the results are shown in Table 3.

table 3

It can be seen from the above table that the sedimentation effect and efficiency of the compounding agent of the invention on the catalyst particles are superior to the commercially available settling agent AH-C80, especially the compounding agent II can reduce the ash content in the oil slurry to less than 50 ppm.

Claims

An oil slurry settling agent characterized in that, by weight, 10 to 50% of a poly(meth)acrylic resin, 5 to 30% of an alkyl quaternary ammonium salt, and 5 to 20% of an alkoxy group Phenolic resin, 25-80% solvent composition.
An oil slurry settling agent characterized by 25 to 35% of a poly(meth)acrylic resin, 15 to 25% of an alkyl quaternary ammonium salt, and 10 to 20% of an alkoxy group by weight percentage. Phenolic resin, 35-50% solvent composition.
A slurry settling agent according to claim 1 or 2, wherein the poly(meth)acrylic resin is one of polyacrylic acid, polymethacrylic acid or a mixture thereof.
The slurry settling agent according to claim 1 or 2, wherein the alkyl quaternary ammonium salt has the formula R 4 NX, wherein R is the same or different C1 to C18 hydrocarbon group, and X is C1-C4 carboxyl group.
The slurry settling agent according to claim 1 or 2, wherein the alkoxyphenol based phenolic resin is an ethoxy novolac resin, a propoxy phenolic resin or a C4 to C9 alkyl phenolic resin. One of them.
A compound slurry settling agent according to claim 1 or 2, wherein the solvent is one or a mixture of ethylene glycol, glycerin or pentaerythritol.
A method for using a compound slurry settler, characterized in that the settling agent is directly added to the slurry for use in an amount of 500 to 2000 ppm and a sedimentation temperature of 80 to 100 °C.