Lower alkane purification method

FIELD: chemistry.

SUBSTANCE: invention relates to a method of purifying lower alkanes from methanol through contact between the raw material and a catalyst which contains aluminium oxide at high temperature and pressure. The method is characterised by that the catalyst used is an aluminiuim-platinum catalyst and contact takes place at temperature of 180-400°C, pressure of 1.5-4.0 MPa, volume rate of supply of material of 0.4-4 h-1 and volume ratio of material : hydrogen equal to 1:(5-900).

EFFECT: invention increases degree of purity of lower alkanes from methanol.

3 cl, 9 ex

 

The invention relates to a method of purification of lower alkanes from methanol and can be used in the refining and petrochemical industry, namely, upon receipt of the hydrocarbons used as solvents in the polymerization processes of olefins.

Know the use of adsorbents to remove impurities methanol and ethers of hydrocarbon streams, such as olefins, natural gas and light hydrocarbon streams. For these purposes a solid porous adsorbents with large surface, such as zeolites, alumina, silica gel, aluminosilicates (RF patent No. 2264855, IPC7B01J 20/18, publ. 27.03.2003; RF patent №2288026, IPC7B01D 53/72, publ. 27.11.2005). The disadvantages of the above adsorbents are low sorption capacity, high temperature regeneration and low selectivity towards methanol.

Known methods of purification of lower hydrocarbons from oxygen-containing impurities, which are used in catalytic purification with the use of catalysts based on silica-alumina zeolites, as well as copper-zincaluminum and zincaluminum catalysts for conversion of methanol (Catalytic purification of hydrocarbon mixtures from methanol. Gospelmusic, Lambiance, Adiastasia etc. /M: World oil, 2007, No. 5, p.30-32). The efficiency of these catalysts, basically, op is Adelaide methanol content in alkane and process conditions (temperature and pressure). However, the drawbacks of these methods is that these catalysts are characterized by low efficiency of methanol and are of limited use for heavy flows due to the conversion of hydrocarbons and rapid deactivation of the catalysts.

The closest in technical essence is a method of purification of hydrocarbon mixtures from methanol (RF Patent No. 2293056, IPC SW 3/22, SS 1/20, publ. 10.02.2007), including contact etanolsoderjasimi hydrocarbon with a zinc-chromium or copper-zinc-chromium catalyst or a catalyst based on zeolite group of pentelow. The contact is carried out at a volumetric feed rate of the raw material 3-15 h-1at a temperature of 220-400°C and pressure up to 1.8 MPa. When using the catalyst for conversion of methanol to hydrocarbons containing 70% of zeolite HZSM-5 and 30% Al2About3the reaction temperature is 400-450°C. the content of methanol in the feedstock is 1.5-5 wt.%, in the purified product from 0.01 to 0.05 wt.%.

The disadvantage of this method is the high residual impurity content of methanol in the hydrocarbon streams.

The objective of the invention is to increase the degree of purification of the lower alkanes from methanol.

To solve this problem is proposed a method of purification of lower alkanes from methanol by contact of the feedstock with a catalyst containing alumina when the appreciation is the R temperature and pressure, at the same time as the catalyst is used aluminium oxide-platinum catalyst and the contact is carried out at a temperature of 180-400°C., a pressure of 1.5 to 4.0 MPa, the space velocity of the raw material 0,4÷4 h-1, a volume ratio of raw materials: hydrogen=1:(5÷900).

Hydrogen can be directed to an adsorption purification from moisture and returned to recycling.

Part of the purified lower alkanes can be used as a diluent cleaned lower alkanes.

As aluminium oxide-platinum catalyst can be used is known, industrially produced catalysts AP-56, FE-62, AP-64, C-2, FE-82 and other catalysts containing platinum and aluminum oxide.

As the lower alkanes can be used fractions of ethane, propane, butane, isobutane, pentane, isopentane and hexane, and others.

For the method of cleaning the lower alkanes from methanol what is new is the use of contact of the hydrocarbons with aluminium oxide-platinum catalyst in the presence of excess hydrogen, which confirms compliance with the patentability criteria of "novelty" and "inventive step". The possibility of applying this method on an industrial cleaning process hydrocarbon fractions confirms the criterion of "industrial applicability".

The method of purification of lower alkanes from methanol is carried out by contacting the purified hydrocarbon fra the Nations of the lower alkanes at a temperature of 180-400°C, a pressure of 1.5 to 4.0 MPa, obymnu feed rate of the raw material 0.4 to 4 h-1a volume ratio of raw materials: hydrogen =1:(5÷900). You can use the pure product (recycle) to dilute the feedstock mass ratio of raw materials: recycling =1:(0,5÷4) and the hydrogen-containing recycle gas to fresh hydrogen in a volume ratio (10÷350):1 respectively.

When the claimed conditions is achieved by clearing fractions of lower alkanes to the content of methanol not more than about 5 ppm., that meets the requirements of polymerization processes.

The implementation of the method is illustrated by the following examples.

Example 1. Cleaning is performed in a reactor with a fixed catalyst bed. As raw materials use propane fraction, containing 3000 ppm. methanol supplied with a bulk velocity of 0.4 h-1the pressure of 1.8 MPa. Raw material is fed into the mixer where it is mixed with dry hydrogen in a volume ratio of 1:100, respectively, and direct contact with the catalyst in the reactor. The process is carried out at a temperature of 280°C on aluminium oxide-platinum catalyst brand FE-62M (TU 38.10173-88). The reaction products from the bottom of the reactor is directed to the selection purified from methanol propane. The reaction products analyzed by hydrocarbon composition by gas chromatography. Analysis of the purified propane shows no admixture of methanol.

<> Example 2. Cleaning is performed in the conditions of example 1, but with the content in the propane fraction 16600 about ppm. of methanol. Raw material is fed into the mixer where it is mixed with dry hydrogen in a volume ratio of 1:200, respectively, and direct contact with the catalyst in the reactor. In purified propane impurity content of methanol is 1.2 ppm.

Example 3. Cleaning is performed in the conditions of example 2. As hydrogen is a mixture of fresh and dried hydrogen and recycle hydrogen, drained and cleaned sorbent NaA from oxygen-containing impurities taken in a volumetric ratio of 1:220, respectively. As catalyst, use of FE-82 (TU 21-149-04610600-99). In purified propane impurity content of methanol is 1.0 ppm.

Example 4. Cleaning is performed in the conditions of example 3, but in the propane fraction containing 33300 about ppm. methanol, add recycle propane mass ratio of 1:2,2, respectively. In purified propane impurity content of methanol is 1.6 ppm.

Example 5. Cleaning is performed in the conditions of example 4, but the process is conducted at a temperature of 340°C, a pressure of 3.0 MPa, with a bulk velocity of 1.0 h-1. As hydrogen is a mixture of fresh and dried hydrogen and recycle hydrogen, drained and cleaned sorbent NaA from oxygen-containing impurities taken in volumetric zootoxin and 1:300. The volumetric ratio of raw materials: hydrogen of 1:400. In purified propane impurity content of methanol is about 1 ppm.

Example 6. Cleaning is performed in the conditions of example 5, but is used as raw material butane-butylene fraction, containing to 25.0 wt.% butylene content of methanol in 53.6 ppm about. In a purified product of the methanol content of about 1 ppm. The content of butylene in purified butane 5% wt.

Example 7. Cleaning is performed in the conditions of example 5, but is used as raw material hexane fraction containing methanol 890 ppm. Cleaning is performed on the catalyst P-64 (TU 2177-011-04749189-95). In a purified product of the methanol content of about 1 ppm.

Example 8. Cleaning is performed in the conditions of example 5, but is used as raw material pentane fraction containing methanol 12000 ppm. Cleaning is performed on the catalyst AP-56 (TU 2177-011-04749189-95). In the purified product of the methanol content of 1.2 ppm.

Example 9. Cleaning is performed in the conditions of example 5, but is used as raw material isopentane fraction with methanol content of 2000 ppm. Cleaning is performed on the catalyst C-2 (TU 2177-009-04706192-00). In a purified product of the methanol content of about 2 ppm.

As seen from the examples, the inventive method allows you to clean hydrocarbons from methanol to curing purity (not more than 5 ppm by vol.). In addition, the proposed method allows you to clean alkanes is not only the co from methanol, but from unsaturated hydrocarbons contained in the treated hydrocarbons.

1. The method of purification of lower alkanes from methanol by contact of the feedstock with a catalyst containing alumina at elevated temperature and pressure, characterized in that the catalyst used aluminium oxide-platinum catalyst and the contact is carried out at a temperature of 180-400°C., a pressure of 1.5 to 4.0 MPa, the space velocity of the raw material 0,4÷4 h-1, a volume ratio of raw materials:hydrogen, 1:(5÷900).

2. The method according to claim 1, characterized in that the hydrogen is directed to an adsorption purification from moisture and return in recycling.

3. The method according to claims 1 and 2, characterized in that the lower part of treated alkanes used as diluent cleaned lower alkanes.



 

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