JPS61125412A - Agent for accelerating settlement of catalyst - Google Patents

Abstract

PURPOSE:To settle a waste fine catalyst suspended in the bottom oil of a fluidized catalytic cracker (FCC bottom oil) utilized as fuel oil, etc. for large marine vessels with a small amt. of the titled agent to be added in a short time by using a polyether compd. obtained by adding alkylene oxide to amines as the agent. CONSTITUTION:Amines are used as the starting substance, and a polyether compd. obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, and styrene oxide to the substance with a well-known method is used as an agent for accelerating the settlement of the catalyst in FCC bottom oil. In this case, the polyether to which 20-100wt% ethylene oxide is added as the alkylene oxide is appropriately used, and the mol.wt. is preferably regulated to 100-200,000. The FCC bottom oil treated with the agent for accelerating the settlement of the catalyst can be used equally as general heavy oil.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an additive for promoting the precipitation of fine waste catalyst suspended in distillation residue oil subjected to fluid catalytic cracking.

[Conventional technology]

Conventionally, normal pressure or vacuum distillation residue oil has been used as fuel oil for large ships, but in recent years, as demand for middle distillates such as kerosene and light oil has increased, comparisons of middle distillate yields have become more important. A highly efficient fluid catalytic cracking method has been developed, and this fluid catalytic cracking distillation residue oil (hereinafter abbreviated as FCC residue oil) has come to be used more and more.

The fluid catalytic cracking method is one of the most popular catalytic cracking methods developed in the early 1940s, and by circulating catalyst particles under high temperature and low pressure, it can crack an extremely wide range of feedstock oils and produce volatile oils with high octane numbers. Manufacture is possible. As a catalyst, 7 with a particle size distribution of several microns to several tens of microns
A liquor alumina-based catalyst is used, which is regenerated during the process and used repeatedly. However, very fine catalyst particles remain suspended in the FCC residual oil.

If FCC residual oil in which fine catalyst particles are suspended is used as a marine fuel, abnormal wear of the fuel pump plunger, piston ring, etc. will occur, and engine trouble will likely occur. The currently used method for removing these fine soot particles is to allow them to settle naturally over several weeks to several months in a heated oven. It hasn't been done yet.

[Problem that the invention seeks to solve]

The method of naturally settling fine catalyst particles suspended in FCC residual oil over a long period of time while heating is not only disadvantageous in terms of energy and time, but also cannot sufficiently remove fine catalyst particles.

The present invention promotes the sedimentation of fine catalyst particles to facilitate their removal, thereby making FCC residual oil as usable as general heavy oil, and in particular, to solve the problems of current FCC residual oil. .

[Means for solving problems]

The present inventors conducted intensive studies to solve the problems associated with FCC residual oil, and as a result, they discovered an additive that can precipitate fine catalyst particles in a short time with a small amount of addition, and completed the present invention.

That is, in the present invention, an alkylene/oxide containing ethylene oxide as an essential component is added to an amine, and the molecular weight is 10.
This is a catalyst precipitation accelerator characterized by containing a polyether compound having a molecular weight of 0 to 200,000 as an active ingredient.

The catalyst precipitation promoter of the present invention is a polyether compound obtained by using an amine as a starting material and adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, or styrene oxide by a known method. .

One or more types of alkylene oxide can be added, but the amount of alkylene/oxide added is 40 to 10
0% by weight, preferably 50-100% by weight of ethylene oxide is suitable. When the ethylene oxide content is less than 40% by weight, the resulting polyether compound has strong lipophilicity and becomes difficult to aggregate fine catalyst particles. The addition type of alkylene oxide may be a block copolymerization type or a random copolymerization type, but a block copolymerization type in which some or all of the ethylene oxide groups are bonded to the terminals is preferred.

The molecular weight of the polyether compound used in the present invention is 1
00-200,000, preferably 200-100,0
It is 00. If the molecular weight is less than or greater than this, the effect as a catalyst precipitation accelerator will decrease, which is not preferable.

The amines used as starting materials for the polyether compound according to the present invention are illustrated below.

b) Amines having one active hydrogen such as dimethylamine, ethylmethylamine, etc.) Amines having two active hydrogens such as methylamine, ethylamine, propylamine, butylamine, amylamine, decylamine, tetradecylamine, Octadecylamine, allylamine, tallow alkylamine, coconut oil alkylamine, 7-cloptylamine, cyclohexylamine, aniline, toluidine, benzylamine, naphthylamine, etc. c) Amines having 3 active hydrogens, such as ammonia, monoethanolamine , jetanolamine, triethanolamine, alkylpropylene diamine, etc. 2) Amines having 4 active hydrogens, such as ethylene diamine, tetramethylene diamine, hexamethylene diamine, phenylene diamine, be/sodine, cyclohexfludiamine, etc. ) Amines having 5 or more active hydrogen atoms, such as diethylenetriami/, triethylenetetrami/, tetraethylenepentami/, polyethyleneimine, etc.

The amount of the catalyst precipitation accelerator of the present invention used is 1 to 1,000 ppm, preferably 100 to 1,100 ppm, based on the FCC residual oil.
It is 0pp. If the amount used is less than ippm, there is almost no effect of promoting catalyst precipitation, and even if the amount used exceeds 2000 ppm, no improvement in the effect is observed, which is economically disadvantageous.

The catalyst sedimentation accelerator of the present invention exhibits a good catalyst sedimentation accelerating effect when added directly to tFcc residual oil, but it is even more effective when added to FCC residual oil after being diluted with a solvent such as quinolene or acetone. Demonstrates excellent effects. Also, F
The catalytic precipitation promoter of the present invention also exhibits good effects on oils that are a mixture of CC residual oil and other heavy oils, such as atmospheric distillation residue oil. Note that the catalyst precipitation promoter of the present invention acts more effectively when mechanical operations such as centrifugation are used together.

[For production]

The reason why the catalyst precipitation accelerator of the present invention can exhibit outstanding effects even when used in a small amount is not clear, but can be considered as follows.

It is essential that the catalyst sedimentation accelerator of the present invention contains a nitrogen atom, which is thought to enhance adsorption to the inorganic catalyst surface. It is thought that the fine catalyst particles on which the sedimentation accelerator has been adsorbed aggregate to gradually become larger lumps, which cause them to settle quickly.

〔Effect of the invention〕

By using the catalyst sedimentation accelerator of the present invention, fine catalyst particles remaining in FCC residual oil can be precipitated in a short time with a small amount of use, so FCC residual oil can be used as much as general heavy oil. It becomes possible to do so. This has immense industrial value in terms of effective utilization of petroleum resources.

〔Example〕

The present invention will be explained by examples.

EXAMPLE The polyether compounds of Samples 1 to 10 shown in Table 1 below were used as catalyst precipitation promoters of the present invention.

Further, for reference, Samples 11 to 12 shown in the same table were used as additives for comparison.

200 ppm of 10% xylene solution (10% acetone solution only for Fly 8) of the catalyst precipitation accelerator shown in Table 1 as an active ingredient.
The mixture was added to the FCC residual oil containing finely divided catalyst particles and stirred for 10 minutes using a homogenizer.

After stirring, the inner diameter is 5.5c++! , a stainless steel cylindrical container with a height of 20 cfR, and fill it to a height of 18 α to 60
It was left standing in a constant temperature bath. After 24 hours, 10c below the liquid level
20 mg was sampled from the In position on a platinum plate.

Alumina and 7 Lika in Kosu/Guru, Journal of the Japan Petroleum Institute, Vol. 2
5, No. 3, pp. 158-161 (1982), quantification was carried out by atomic absorption method according to the method described in K.

Nine comparative additives were also tested in the same manner.

In addition, silica 2.11 was contained in the sample FCC residual oil before the test.
00ppm and alumina 850ppm were contained.

The results obtained are summarized in Table 2.

Table 2 Notes 1) As is clear from the test results obtained by adding a 10% A7 solution, the catalyst precipitation accelerator of the present invention can quickly remove fine catalyst particles in FCC residual oil with a small amount added. It can be seen that this additive has an excellent sedimentation promoting effect compared to other additives.

Claims (1)

[Claims] 1. An alkylene oxide containing ethylene oxide as an essential component is added to an amine, and the molecular weight is 100 to 200.0.
1. A catalyst precipitation accelerator characterized by containing a polyether compound of No. 00 as an active ingredient. 2. The catalyst precipitation promoter according to claim 1, wherein the alkylene oxide is ethylene oxide, propylene oxide, butylene oxide, or styrene oxide, and 40 to 100% by weight of the alkylene oxide added is ethylene oxide.