Method for catalytical purification of paraffin hydrocarbons from methanol admixtures

FIELD: chemistry.

SUBSTANCE: invention refers to the method of purification of paraffin hydrocarbons from methanol admixtures. The said purification is carried out in the presence of hydrogen on the catalyst containing one of the metal selected from Ni and Pd applied on the inert carrier at temperature 30-100°C, mole excess hydrogen : methanol in the range (5-50): 1 and volume hydrocarbons feed rate 1-6 hrs.-1.

EFFECT: simplifying and cheapening of the process.

1 cl, 9 ex, 1 tbl

 

The invention relates to oil, gas and petrochemical industry, to processes for obtaining and using the lower paraffin hydrocarbons, namely the process of purification from impurities methyl alcohol (methanol).

The presence of methanol in the product paraffinic hydrocarbons degrade their quality as raw material for petrochemical synthesis, and decreases their price for export. For example, for propane for delivery on the export of standardized methanol content of not more than 50 ppm.

A known method of purification of hydrocarbons by washing with water ["Propane exports", Perm news, No. 45(1062) dated 10.11.2000,]. In this case the residual methanol content, for example, propane, even with 10-20-fold excess of water is not reduced below 100 ppm. In addition, the strong flooding of hydrocarbons requires additional costs upon drying. There is a method of Hydrotreating of petroleum products on the Al-Co-Mo catalyst [Reference oil Ed. Scholarone.com. L.: Chemistry, 1978, vol. 1, s]. The process is conducted at elevated temperatures of 300-400°C and a pressure of 3-4 MPa, accompanied by the cracking part of the oil.

Closest to the claimed method is catalytic purification of light gasoline fractions of gas condensate on imported copper catalyst for methanol synthesis [Aksakov. "Technology training gas conden the ATA", Neftgazpromyshlennost, 6(18) September 2005, p.46-48] (Prototype). The disadvantages of this method are the use of expensive imported catalyst and high energy costs, loss of hydrocarbons by cracking and pitch at elevated temperature.

The objective of the proposed method is simpler and cheaper technology process.

The problem is solved by the use of domestic catalysts for hydrogenation processes containing the active metals Ni, Pd, deposited on an inert carrier.

Characterization of catalysts

Catalyst Nickel on kieselguhr" [Handbook of Neftekhimik edited Scholarone.com, vol. 1, s] is used for the hydrogenation of organic compounds of different classes, for the purification of gases and vapors from the impurities of unsaturated compounds.

AppearanceTablet black
The diameter and height of the tablets mm3.5 to 4.5
Bulk density, kg/m31100
The specific surface Sbeats.10-3m2/kg100-150
The surface of the metal Nickel S beats.·10-3m2/kg13-15
Pore volume Vp·10-3m2/kg0,4
Mechanical strength:
crush strength "by forming a", N/pill
78-118
Attitude strength crushing "on the side" to strength the crushing "forming"2,0-2,5

The catalytic hydrogenation of aromatic hydrocarbons - palladium deposited on alumina [Reference oil Ed. Scholarone.com, vol. 1, s], is used in one-step process of hydrogenation of phenol to cyclohexanone.

AppearanceGray granules
The chemical compositionPalladium deposited on a
aluminum oxide
The size of granules3-5
Bulk density, kg/m3500

The use of these catalysts for the process of purification of hydrocarbons from methanol unknown and are not described in literature.

p> Cleaning paraffin hydrocarbons by the present method is carried out at low temperatures (30-100°C in the liquid phase.

The invention disclosed provides specific examples.

All the examples are summarized in table. As a model of paraffin hydrocarbon is taken n-heptane.

Example 1. In the tubular reactor is loaded with 100 cm3catalyst "Nickel on kieselguhr". The catalyst restore in a stream of hydrogen at 250°C for 12 hours to remove moisture. The temperature was then reduced to 50°C. Over the catalyst miss n-heptane, containing 0.25% (2500 ppm) of methanol with a bulk velocity of 2.0 h-1and a molar excess of hydrogen to methanol, 50:1. The content of methanol in n-heptane after the reactor is 0,0025% (25 ppm).

Example 2. Purification of n-heptane from methanol is performed under the conditions described in example 1.

Example 3. Purification of n-heptane from methanol is performed under the conditions described in example 1.

Example 4. Purification of n-heptane from methanol is performed under the conditions described in example 1.

Example 5. Purification of n-heptane from methanol is performed under the conditions described in example 1, the catalyst is palladium on Al2O3" (a 0.5% Pd / γ-Al2O3).

Example 6. Purification of n-heptane from methanol is performed under the conditions described in example 5.

Example 7. Purification of n-heptane from the methanol is carried out in us what the conditions, described in example 5.

Example 8. Purification of n-heptane from methanol is performed under the conditions described in example 5.

Example 9. (The prototype.) Cleaning of light gasoline fractions of gas condensate from methanol spend on imported copper-containing catalyst at a temperature of 270°C, flow rate 30000 h-1(gas) or 1, 3 h-1(liquid). The methanol content after cleaning is 50 ppm, loss of hydrocarbons to 12%.

Purification of hydrocarbons from methanol
No.CatalystCleaning requirementsThe methanol content, ppmLoss of hydrocarbons, wt.%
P, MPaT, °CV, h-1The molar excess of N2:CH3HE, mol:molBefore cleaningAfter cleaning
1Nickel
the diatomaceous earthBar.502,050:1250025UTS.
2Nickel
the diatomaceous earthBar.505,035:1250014UTS.
3Nickel
the diatomaceous earthBar.501,050:15UTS.
4Nickel
the diatomaceous earthBar.503,04:1250051UTS.
5Palladium on
Al2O3Bar.305,016:119005UTS.
6Palladium on
Al2O3Bar.1002,625:119006UTS.
7Palladium on
Al2O3Bar.506,05:1190012UTS.
8Palladium on
Al2O3Bar. 507,016:1190051UTS.
9
(FR.)
Copper
containingBar.2701,3-200050to 12.0

When the volumetric feed rate of the raw material for more than 6 h-1(example 8) and a molar excess of hydrogen to methanol less than 5.0 (example 4) was observed breakthrough of methanol in the raw material is more than 50 ppm. Increasing the molar excess of hydrogen to methanol over 50:1, to reduce the volumetric feed rate of less than 1 h-1and to raise the temperature in the reactor of more than 100°C, i.e. to increase the energy consumption, it is not economically feasible.

As seen from the above examples, the inventive method allows cleaning hydrocarbons from methanol in a very "soft" conditions, i.e. practically at room temperature and atmospheric pressure, which dramatically skiauteretasis costs and eliminates loss of hydrocarbons at high depth cleaning. The performance of the claimed method is more than 4 times higher performance by a known method.

Method for catalytic cleaning of paraffin hydrocarbons from admixture of methyl alcohol, wherein the cleaning is performed in the presence of hydrogen on the catalyst containing one of the metals of groups: Ni, Pd, deposited on an inert carrier at a temperature of 30-100°C., a molar excess of hydrogen: methanol (5-50):1 and a space velocity of hydrocarbon 1-6 h-1.



 

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10 cl, 12 ex, 2 tbl

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8 cl, 5 tbl, 9 ex

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