JPH01207389A - Purification of hydrocarbon and treating agent therefor - Google Patents

Abstract

PURPOSE:To accomplish the purification of hydrocarbon by bringing a hydrocarbon containing nitrogen compounds into contact with a treating agent prepared by carrying phosphoric acid on a carrier to remove said nitrogen compounds in high efficiency without influencing the compounds readily reactive with hydrogen present in said hydrocarbon. CONSTITUTION:Firstly, a treating agent is prepared by carrying e.g., 5-75wt.% of phosphoric acid (e.g., phosphorus pentoxide) on a carrier. Secondly, a hydrocarbon containing nitrogen compounds is brought into contact with said treating agent, thus enabling said nitrogen compounds to be removed without influencing the compounds readily reactive with hydrogen (e.g., olefins, aromatics) contained in said hydrocarbon irrespective of basic or nonbasic, or water-soluble or water- insoluble state.

Description

[Detailed description of the invention] Object of the invention (m-1) The hydrocarbon raw material contains basic nitrogen compounds such as amines, anilines, pyridines, quinolines, amides, diazas, or pyrrole. Contains non-basic nitrogen compounds such as carbazoles, nitriles, etc., and when a catalytic reaction is performed using these as raw materials, it may cause deterioration of the catalyst and a decrease in the yield of the reaction product, and carbonization may occur. It causes blue color and gummy formation of hydrogen products.

The present invention relates to a method for purifying hydrocarbons by removing nitrogen compounds from the hydrocarbons containing nitrogen compounds, and a treatment agent for purification.

[The method most commonly used in the past to remove nitrogen compounds contained in hydrocarbons is to use high-pressure hydrogen to ammonify and remove nitrogen compounds.

However, in this method, if the raw material hydrocarbon contains compounds that easily react with hydrogen, such as olefins and aromatics, they are also hydrogenated, so it is difficult to measure whether they can be used effectively.
Another drawback is that hydrogen is consumed unnecessarily. In addition, some hydrocarbons undergo hydrocracking to produce gases with low added value such as methane and ethane.

Are there other removal methods such as cleaning with wood or acid solutions to remove nitrogen compounds?

This method can be applied to basic or water-soluble nitrogen compounds, or cannot be applied to non-salt nof or poorly water-soluble nitrogen compounds.

As methods for adsorbing and removing nitrogen compounds, methods using zeolites (Japanese Patent Application Laid-open No. 5O-18578) and methods using titanium oxide/silica (Japanese Patent Application Laid-open No. 6O-40195) are known, but basic nitrogen compounds However, since the adsorption capacity for non-basic nitrogen compounds is small, the nitrogen concentration cannot be lowered sufficiently and the treatment agent must be regenerated more frequently.

Kajiyo. According to the present invention, nitrogen compounds contained in hydrocarbons can be converted into basic or non-basic compounds without affecting compounds that easily react with hydrogen, such as olefins and aromatics contained in raw material hydrocarbons. It is an object of the present invention to provide a method for efficiently removing and purifying a substance, regardless of whether it is water-soluble or water-insoluble, and a purification treatment agent.

1. Structure of the invention , in order to.

The method for purifying hydrocarbons according to the present invention is characterized in that a hydrocarbon containing a nitrogen compound is brought into contact with a treatment agent comprising phosphoric acid supported on a carrier.

The supported phosphoric acid undergoes transformation depending on the temperature at which it is used, becoming orthophosphoric acid, pyrophosphoric acid, or metaphosphoric acid.
Any form can be used and is not particularly limited.

As the carrier, it is preferable to use porous substances such as silica, diatomaceous earth, alumina, silica alumina, zeolite, and activated carbon, which are commonly used as carriers for catalysts and processing agents, but are not limited to these.

It is sufficient that phosphoric acid is immobilized and supported on the carrier as described above, and the larger the amount of phosphoric acid supported, the larger the amount of nitrogen compounds adsorbed. The amount supported varies depending on the carrier used, but generally about 5 to 75% by weight of phosphorus pentoxide is supported.

Impregnation methods, kneading methods, etc. are generally used as supporting methods.
It is not limited to et.

The processing temperature for hydrocarbons containing nitrogen compounds is room temperature ~
400°C is suitable. The higher the temperature, the higher the removal rate of nitrogen compounds, or the possibility that compounds other than nitrogen compounds may react.

Does the removal rate of nitrogen compounds change depending on LH3V?
Practically, the usable range is 100 to 0.1/hr.

As the apparatus, a conventional fixed bed adsorption device is preferably used, but a fluidized bed, a moving bed, a stirring tank, etc. can also be used.

When using a carrier other than activated carbon, the treatment agent used in the method of the present invention, which is made by supporting phosphoric acid on a carrier, for removing nitrogen compounds from hydrocarbons, is heated to a high temperature with an oxygen-containing gas. Through treatment, nitrogen compounds can be burned, removed, regenerated, and reused.

The hydrocarbons to which the method of the present invention is applied are not particularly limited as long as they contain nitrogen compounds, but are preferably straight-run oils, catalytic cracking oils such as FCC oils, pyrolysis oils, or coals such as naphthalene. Examples include hydrocarbon oils obtained from.

Examples of processes to which the present invention is preferably applied include the following.

■As a pretreatment when modifying raw materials: When reacting a naphthalene mixture with an alkylating agent to produce various alkylnaphthalenes, silica alumina, crystalline silicate, zeolite, ion exchange resin, heteropolyacid can be used as a catalyst. A solid acid such as aluminum chloride or a liquid acid such as an inorganic acid is used, but since these are all poisoned by nitrogen compounds and lose their activity, it is necessary to frequently replace or regenerate the catalyst. When naphthalenes are treated with hydrogen, a portion of the naphthalene rings become tetralin rings, which is undesirable as it leads to loss of raw materials and an increase in hydrogen consumption.According to the method of the present invention,
Nitrogen compounds can be easily removed without changing the form of the raw material.

■As a method of stabilizing the content of raw materials: Catalytic cracking oil may form gums or become colored due to the nitrogen compounds contained therein polymerizing and oxidizing. Hydrogen consumption μ increases, making it uneconomical. In the method of the present invention, nitrogen and R compounds can be easily removed without consuming hydrogen, and storage stability can be improved.

Amines, anilines, pyridines in hydrocarbon raw materials,
Basic nitrogen compounds such as quinolines, amides, and diazas are acids/II! It reacts with the supported phosphoric acid through a group neutralization reaction and is immobilized on the carrier as a phosphoric acid compound. On the other hand, although the behavior of non-basic nitrogen compounds is not necessarily clear, virols and carbazoles polymerize on supported phosphoric acid to form resins, and nitriles polymerize on monosyric acid supported by trace amounts of moisture in the raw materials. It is presumed that it is hydrolyzed and converted into basic nitrogen compounds such as ammonia and amide, and then removed.

Examples 1 to 8 Phosphoric acid on a lithographic plate was diluted with distilled water to give a phosphoric acid concentration of 80% by weight. This is impregnated into a predetermined amount of carrier.

After drying, it was baked at 350°C to prepare a processing agent.

The resulting treatment agent was 100n! L is 5U with inner diameter 16.1mm
S5! Fill the adsorber and reduce the nitrogen compound N concentration to 410
Weight ppm<330 ffi m p p m b
A 95% by weight naphthalene oil containing <basic nitrogen compounds, the rest being non-basic nitrogen compounds) was poured to measure the Nei degree in the produced oil. The results are shown in Table 1. No conversion of naphthalene was observed in any of the treatments.

Comparative Examples 1 to 5 Processing agents not carrying phosphoric acid were also treated in the same manner as in the above examples, and the N6 degree of the treated oil was measured.

The results are shown in Table 1.

(Margin below) Table 1 Comparative Example 6 In order to investigate the effect of ordinary hydrorefining, the naphthalene oil used in Example 1 was treated with 35%
0℃, 20kg/am2G, LH3V=0.5 (1/h
The treatment was carried out while flowing hydrogen at 25 t/hr.

The N concentration of nitrogen compounds contained in the obtained product oil was 10 ppm by weight, or 32% by weight of the raw material naphthalene had been converted to tetralin.

Examples 9-13 120 ppm by weight of N (of which 11011 ppm is basic,
Catalytic cracking oil (LC
The N concentration in the produced oil was measured by flowing it in the same manner as in Example 1. The results are shown in Table 2.

Table 2 Example 14 The same test as in Example 1 was conducted except that the firing temperature of the treatment agent used in Example 1 was changed. The results are shown in Table 3.

Table 3 Comparative Example 7 100ml of a 10% by weight phosphoric acid aqueous solution was added to 100ml of the LCO fraction used in Example 9, and after shaking at room temperature for 1 hour, the N concentration contained in the LCO fraction was measured. did. N
The concentration was 113 ppm by weight.

Example 16 The treatment agent used in Example 1 was treated at 600% under the same conditions as Example 1.
N5 degree in the produced oil when oil is passed for an hour is 410 heavy Jipp
It was m. This treatment agent was regenerated with air at 550°C. The treatment agent after regeneration was tested in the same manner as in Example 1, and 1
When the N concentration in the produced oil obtained after 00 hours was measured, it was found to be 23 ppm by weight, indicating that it was due to regeneration or circulation.

Example 17 Adding virol, carbazole and indole to benzene with N
Simulated raw materials were prepared and tested in the same manner as in Example 1, to which 20 ppm by weight of E was added.

The N concentration in the produced oil obtained after 100 hours was measured and found to be 3 ppm by weight, indicating that it was also effective in removing non-basic nitrogen compounds.

Comparative Example 8 A test similar to Example 17 was conducted using 5iOz that did not support phosphoric acid. When the N concentration in the produced oil obtained after 20 hours was measured, it was found to be 58 ppm.

Effects of the Invention ■ Nitrogen compounds in hydrocarbons, regardless of whether they are basic or non-basic, water-soluble or water-insoluble, can be removed to a high degree.

■No need to use hydrogen.

■There is almost no decomposition or hydrogenation of hydrocarbons, and it is effective as a pretreatment or storage stabilization treatment for various hydrocarbons.

■Can be processed under relatively mild conditions and consumes little utility.

■Since the adsorption capacity is extremely large, equipment costs are low.

Claims (1)

[Scope of Claims] 1. A method for purifying hydrocarbons, which comprises bringing a hydrocarbon containing a nitrogen compound into contact with a treatment agent comprising phosphoric acid supported on a carrier. 2. A hydrocarbon purification treatment agent comprising phosphoric acid supported on a carrier.