JPS6359726B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] 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 diesel oil has increased, middle distillate A fluid catalytic cracking method with a relatively high yield has been developed, and this fluid catalytic cracking distillation residue oil (hereinafter abbreviated as FCC residue oil) has come to be used. Fluid catalytic cracking is a type of catalytic cracking method developed in the early 1940s, and it cracks a wide range of feedstock oils by circulating catalyst particles under high temperature and low pressure to produce volatile oil with a high octane number. is possible. As the catalyst, a silica-alumina catalyst having a particle size distribution of several microns to several tens of microns is used, and is regenerated during the process and used repeatedly.
However, very fine catalyst particles remain suspended in the FCC residual oil. When FCC residual oil containing suspended fine catalyst particles is used as marine fuel, it can cause abnormal wear of the fuel pump plunger and piston rings, which can easily cause engine trouble. Currently, the method used to remove these fine catalyst particles is to allow them to naturally settle in a heated tank over several weeks to several months, and no attempts have been made to promote sedimentation using additives or the like. . [Problems to be solved by the invention] The method of naturally settling fine catalyst particles suspended in FCC residual oil over a long period of time while heating them is as follows:
This method is not only disadvantageous in terms of energy and time, but also cannot remove fine catalyst particles sufficiently. The present invention aims to solve the problems of the current FCC residual oil by promoting the sedimentation of fine catalyst particles to facilitate their removal and making it possible to use the FCC residual oil in the same way as general heavy oil. . [Means for Solving the Problems] As a result of intensive studies aimed at solving the problems of FCC residual oil, the present inventors have discovered an additive that can precipitate fine catalyst particles in a short period of time with a small amount added. They discovered a new agent and completed the present invention. That is, the present invention provides a silica-alumina catalyst precipitation in residual oil, which is characterized by adding alkylene oxide containing ethylene oxide as an essential component to amines and containing a polyether compound having a molecular weight of 100 to 200,000 as an active ingredient. It is an accelerator. The catalyst precipitation promoter of the present invention is a polyether compound obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, or styrene oxide to an amine as a starting material by a known method.
Although one or more alkylene oxides can be added, it is suitable that ethylene oxide accounts for 40 to 100% by weight, preferably 50 to 100% by weight of the amount of alkylene oxide added. When the ethylene oxide content is less than 40% by weight, the resulting polyether compound has strong lipophilic properties and becomes difficult to aggregate fine catalyst particles. The addition type of alkylene oxide may be either 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 100 to 200,000, preferably 200 to 100,000. 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. (b) Amines having two active hydrogen, such as methylamine, ethylamine, propylamine, butylamine, amylamine, decylamine, tetradecyl Amine, octadecylamine, allylamine, tallow alkylamine, coconut oil alkylamine, cyclobutylamine, cyclohexylamine, aniline, toluidine, benzylamine, naphthylamine, etc. (c) Amines having 3 active hydrogens, such as ammonia, monoethanolamine , diethanolamine, triethanolamine, alkylpropylene diamine, etc. (d) Amines having 4 active hydrogens, such as ethylenediamine, tetramethylene diamine, hexamethylene diamine, phenylene diamine, benzidine, cyclohexyl diamine, etc. (e) Active hydrogen Amines having 5 or more, e.g.
Diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine, etc. The amount of the catalyst precipitation accelerator of the present invention used is 1 to 2000 ppm, preferably 100 to 2000 ppm, based on the FCC residual oil.
It is 1000ppm. If the amount used is less than 1 ppm, there is almost no effect in promoting catalyst precipitation, and on the other hand, if it is used in excess of 2000 ppm, no improvement in the effect is seen, which is economically disadvantageous. The catalyst sedimentation accelerator of the present invention exhibits a good catalyst sedimentation accelerating effect when added to FCC residual oil as it is, but it is even more effective when added to FCC residual oil after being diluted with a solvent such as xylene or acetone. be effective. Furthermore, the catalytic precipitation promoter of the present invention exhibits a good effect on oils that are a mixture of FCC residue oil and other heavy oils, such as atmospheric distillation residue oil. It should be noted that when mechanical operations such as centrifugation are used in combination, the catalyst precipitation accelerator of and acts more effectively. [Function] 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 precipitation accelerator of the present invention contains a nitrogen atom, which is thought to improve adsorption to the surface of the inorganic catalyst. In addition, due to the effect of hydrophilic ethylene oxide chains,
It is thought that the fine catalyst particles on which the sedimentation accelerator has been adsorbed aggregate and gradually become larger lumps, which quickly settle. [Effects of the Invention] By using the catalyst sedimentation accelerator of the present invention, fine catalyst particles remaining in FCC residual oil can be sedimented in a short time with a small amount of use. It becomes possible to use it on a par with heavy oil. This has immeasurable industrial value in terms of effective utilization of petroleum resources. [Example] The present invention will be explained with reference to an example. Examples Polyether compounds of samples Nos. 1 to 10 shown in Table 1 below were used as catalyst precipitation accelerators of the present invention.
In addition, sample Nos. 11 to 12 shown in the same table for reference.
was used as an additive for comparison. A 10% xylene solution (10% acetone solution only for No. 8) of the catalyst precipitation accelerator shown in Table 1 is used as an active ingredient.
It was added in an amount of 200 ppm to the FCC residual oil containing fine catalyst particles, and stirred for 10 minutes using a homogenizer. After stirring,
It was placed in a stainless steel cylindrical container with an inner diameter of 5.5 cm and a height of 20 cm to a height of 18 cm and left in a constant temperature bath at 60°C. After 24 hours, from a position 10 cm below the liquid level,
ml was sampled in a platinum plate. Alumina and silica in this sample were quantified by atomic absorption spectrometry according to the method described in Journal of the Japan Petroleum Institute, Vol. 25, No. 3, pp. 158-161 (1982). Comparative additives were also tested in the same manner. In addition, silica was present in the sample FCC residual oil before the test.
It contained 2100ppm and 850ppm alumina. The results obtained are summarized in Table 2.

【table】

【table】

[Table] As is clear from the above test results, the catalyst precipitation accelerator of the present invention can be used in a short period of time with a small amount added.
It can be seen that the fine catalyst particles in FCC residual oil can be precipitated, and that it has a better sedimentation promoting effect than 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 100.
A silica-alumina-based catalyst precipitation accelerator in residual oil, characterized in that it contains a polyether compound of 200,000 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.