The method of obtaining hydrocarbon propellants

 

(57) Abstract:

The invention relates to a technology for environmentally friendly hydrocarbon gases as propellants. In the process of rectification of hydrocarbons produce a mixture of hydrocarbons of a given composition with excess saturated vapour pressure corresponding to the excess pressure of saturated vapors of hydrocarbon propellants. The selected hydrocarbon mixture is subjected to a preliminary cleaning and deodorization on charcoal. Then carry out the drying, cleaning, deodorization placed on the successive layers of zeolite NaA, CaA, NaX. Regeneration of zeolites provide nitrogen or dried and purified hydrocarbon gas. The improved method will allow you to get high quality products, to expand the range of raw materials used and reduce operating costs. 4 C.p. f-crystals, 1 Il.

The invention relates to a technology for environmentally friendly hydrocarbon gases, propellants, and can be used in gas, oil, refining and petrochemical industries, as well as in household chemicals, medicine and perfumery.

The closest in technical sushnosti in the article "Modern state and prospects for the use of hydrocarbon propellants in the capitalist countries" (overview, series: "the Chemical industry abroad", vol. 1, S. 20 - 43).

The essence of the method lies in the fact that is used as raw material gases, gas processing, refineries and petrochemical plants (gas fractionation, cracking, reforming, isomerization products). From the source of gas release fraction of liquefied hydrocarbons from propane to pentane, which is the raw material for the production of hydrocarbon propellants. After directly hydrocarbon mixture is subjected to low-temperature fractionation to isolate propane, n-butane, isobutane. The obtained components are thoroughly cleaned of traces of catalyst, unsaturated and sulfur compounds. For example, the propane fraction after treatment with acid washed with an alkaline solution to get rid of traces of acid, then subjected to stepwise distillation to remove the remaining odorous substances and drying for dehydration. Then peeled and dried hydrocarbons are mixed to prepare mixtures with a given saturated vapor pressure.

The disadvantages of this method are:

high operating costs;

get propellants have a slight odor;

This object is achieved in that in a method of producing hydrocarbon propellants, including rectification of hydrocarbons, cleaning, deodorization and drying, in the process of rectification produce a mixture of hydrocarbons of a given composition with excess saturated vapour pressure corresponding to the excess pressure of saturated vapors of hydrocarbon propellants, and subjected to pre-cleaning and deodorization on charcoal and drying carried out on synthetic zeolites.

In addition, after the preliminary cleaning and deodorization carry out the dehydration of hydrocarbon raw materials, cleaning and deodorization on synthetic zeolites with subsequent regeneration of the zeolites.

Moreover, drying, cleaning and deodorization is carried out by passing a mixture of hydrocarbons by placing successive layers of zeolite NaA, CaA and NaX. The regeneration of zeolites provide nitrogen or dried and purified hydrocarbon gas.


pre-treatment mixture selected after distillation of hydrocarbons on activated carbon;

dehydration of synthetic zeolites;

conduct after preliminary cleaning and deodorization of drying, cleaning and deodorization of synthetic zeolites with subsequent regeneration of zeolites;

implementation drying, cleaning and deodorization by passing a mixture of hydrocarbons by placing successive layers of zeolite NaA, CaA and NaX;

use as a regeneration gas of nitrogen or dried and purified hydrocarbon gas.

In the distillation of hydrocarbons are first separated light hydrocarbons and heavier hydrocarbons, C3+bheading further rectification, where for a given mode receive hydrocarbons not in the form of individual products, and in the form of a mixture of hydrocarbons with excess saturated vapour pressure corresponding to the excess pressure of saturated vapors of hydrocarbon propellants.

Thus, as a feedstock to produce a hydrocarbon propellants, you can use any uglevodno after rectification of the mixture of hydrocarbons on activated carbon prevents rapid decontamination and prolong the service life of synthetic zeolites, and improve the quality of the product due to the absorption of the activated coal tar, light sulfur compounds, RSR, COS, and unsaturated hydrocarbons.

Deep dehydration and fine purification of the hydrocarbon mixture is carried out by passing the latter through the layers of zeolite NaA, CaA and NaX. The first movement of the hydrocarbon mixture is a layer of zeolite NaA, then a layer of zeolite CaA and a layer of zeolite NaX. The zeolite NaA provides deep drying of a hydrocarbon mixture, the zeolite CaA absorbs light sulfur compounds such as hydrogen sulfide, methyl mercaptan and ethyl mercaptan, and zeolite NaX removed all the mercaptans and sulfides. Moreover, the ratio of the layers is calculated in each individual case depending on the composition and requirements of the finished product, to maximize the capacity of each layer of the sorbent on the extracted component. Using this combination of layers NaA, CaA and NaX allows you to manifest a new quality of the combined layer to limit the adsorption of hydrocarbon, C3+Band this leads to increased dynamic capacity of zeolites on the extracted component to increase the degree of selectivity purification of a hydrocarbon mixture, Uli, clean and dry hydrocarbon gas reduces operating costs, because the regeneration gas required for the process of purging equipment and thermal regeneration of zeolites, prepared directly on the plant producing propellants.

The proposed method is carried out on the installation, the technological scheme of which is contained in the drawing.

Of the liquefied gas in a distillation installation, including heat and mass transfer apparatus (1) and the receiving node of the composition of propellants (2), get a propane-butane-isobutane mixture of a given composition with excess saturated vapour pressure corresponding to the excess pressure of saturated vapors of hydrocarbon propellants.

The resulting mixture was fed in alternately operating the charcoal adsorbers (3, 4), filled with activated charcoal. After the layer of activated charcoal from the bottom up, the mixture is purified from unsaturated compounds, wax compounds and partially from sulfur compounds. From carbon adsorbers (3, 4) hydrocarbon mixture is fed through a filter (5) from bottom to top in the adsorbers (6, 7, 8), layers filled with synthetic zeolites brands NaA, CaA, NaX. This combination of layers of zeolites provides deep dehydration, fine purification from sulfur compounds and DEZ compounds 0,00001% leaving the adsorbers (6, 7, 8) and is output from the filters (9, 10) in the form of finished product (11). Regeneration of activated carbon adsorbers (3, 4) are known manner, for example water vapor. Regeneration of zeolites in the adsorbers (6, 7, 8) carry out gas, having passed the site preparation (12). As regeneration gas and cooling use technical nitrogen or dried and purified hydrocarbon gas. The adsorbers (6, 7, 8) are such that at the stage of adsorption, regeneration and cooling is one apparatus.

The obtained hydrocarbon propellants due to their physical-chemical parameters conform to 39-892-93:

Excessive vapor pressure, MPa - 0,33 - 0,4

Mass fraction, %:

Ethan, not more than - 0.5

The amount of propane, butane, isobutane, not less than 99,0

Pentane is not more than - 0.5

Unsaturated hydrocarbons, not more than 0.02

Sulfur compounds, not more than 0,0005

Non-volatile matter not more than 0,001

Water, not more than 0,01.

Example 1. To obtain hydrocarbon propellants required for aerosol packaging products company, ask the excess pressure of 0.33 - 0.36 MPa and the following composition, mass fraction, %:

Propane, butane, isobutane, the NISTO compounds, not more than 0,00001

Mass fraction of solids, not more 0,00002

Mass fraction of water, not more - is 0.0002.

The necessity of choosing the composition of the propellants, and the excess vapor pressure due to the specifics of the preparation and usage of a large range of products in aerosol packaging (perfumes, cosmetics, household chemistry, medicine, varnishes, paints and so on).

In heat and mass transfer apparatus (1) preliminary preparation of raw materials direct hydrocarbon gases of the following composition (mass content, %): methane - traces; ethane 3,70; propane 33,0; propylene 0,7; isobutane 16,70; n-butane 33,60; isopentane 6,50; n-pentane 5,8; the water content is 0.22 g/m3; sulfide 0,0044 g/m3; mercaptans 0.0015 g/m3; wax substances 4 mg/100 ml At the temperature of the top of the machine on level 41 - 42oC and a pressure of 2.1 MPa remove light components (mass content, %): methane - traces; ethane 16,2; propane 72,5; propylene 0,7; isobutane 6,2; n-butane 4,8; pentane 0.05 of raw materials. The thus prepared raw material from a bottom of heat and mass transfer apparatus (1) arrives at the receiving node of the composition of propellants (2), where the temperature of the top of 58.8oC and davlenie 0,3; isobutane 23,22; n-butane 47,92; the amount of pentane to 0.3; and water 0.20 g/m3; sulfide 0,0040 g/m3; ethyl mercaptan 0.001 g/m3; butylmercaptan 0.0004 g/m3; wax 3 mg/100 ml. Excess vapor pressure equal to 0.35 MPa, which corresponds to THE 39-92-93 hydrocarbon propellant.

The obtained hydrocarbon mixture is fed into one of the adsorbers (3, 4), where activated charcoal brand AG-2 are completely removed unsaturated hydrocarbons, wax substance and partially sulfur compounds.

Further, the hydrocarbon mixture is purified by the filter (5) from the smallest particles of activated carbon and is sent in one of the adsorbers (6, 7, 8) filled with synthetic zeolite NaA, CaA, NaX. The ratio of layers CaA : NaX - 2 : 1.

Deep dehydration and fine purification of the hydrocarbon mixture is carried out by threadarray scheme, each of which operates sequentially in the mode of adsorption, regeneration and cooling.

The hydrocarbon mixture in a steady stream speed 0,0012 m/s at a pressure of 0.85 MPa and a temperature of 45oC served in the adsorber (6). At this time, the adsorber (7) operates in the regeneration mode, and the adsorber (8) in the cooling mode.

After possederant water 0.0005 g/m3and sulfur compounds 0,000053 g/m3(within 0.00001 wt.%).

The obtained hydrocarbon propellant is cleared from the zeolite dust on the filters (9, 10) and sent (11) to the warehouse of finished products. According to its physico-chemical parameters obtained propellant corresponds to THE 39-892-93.

If you increase the mass content of sulfur compounds over 0,00001% of the material in the adsorber (6) stop and flip it in the regeneration mode. The supply of raw materials is carried out in the adsorber (8), which is regenerated and cooled. The adsorber (7) switch to the cooling mode.

Regeneration of spent adsorbent conduct prepared by the regeneration gas is heated in the furnace up to 320 - 350oC. the Adsorber (6) is disconnected from the main stream of a hydrocarbon mixture, which is extracted by cold regeneration gas in the adsorber (8), switched in a cycle of adsorption.

When stabilization of the temperature at the outlet of the adsorber at the level of 300 - 315oC regeneration is completed. The adsorber (6) is switched to cooling.

Example 2. To obtain hydrocarbon propellants required for aerosol packaging products company, ask the excess pressure of 0.38 - 0.4 MPa and the following composition, mass fraction of torodi - Missing

Mass fraction of sulfur compounds, not more than 0,00001

Mass fraction of solids, not more 0,00002

Mass fraction of water, not more - is 0.0002.

In heat and mass transfer apparatus (1) preliminary preparation of raw materials direct hydrocarbon gases of the following composition (mass content, %): Ethan 2,30; of 36.75 propane; isobutane 12,3; n-butane 24,1; isopentane 7,15; n-pentane - 8,65; C6+B8,75; the water content of 0.25 g/m3hydrogen sulfide 0.004 g/m3, mercaptans 0.0015 g/m3, wax 5 mg/100 ml At the temperature of the top of the apparatus 40 and 41oC and a pressure of 2.1 MPa remove light components (mass content, %: Ethan 30,7; propane 65,5; isobutane 2,2; n-butane to 1.59; pentane 0,01) from raw materials. The thus prepared raw material from a bottom of heat and mass transfer apparatus (1) arrives at the receiving node of the composition of propellants (2), where the temperature of the top of 55.4oC and a pressure of 0.9 MPa obtain a hydrocarbon mixture of a given composition (mass content, %): Ethan 0,49; propane 35,83; isobutane 21,28; n-butane 42,1; the amount of pentane 0.3, the water content of 0.2 g/m3; sulfide 0,0031 g/m3; ethyl mercaptan 0,0006 g/m3; butylmercaptan 0.0008 g/m3; wax 3 mg/100 ml overpressure saturated hydrocarbon mixture is fed into one of the adsorbers (3, 4), where activated charcoal brand AG-2 are completely removed wax substance and partially sulfur compounds. Further, the hydrocarbon mixture is purified by the filter (5) and is sent in one of the adsorbers (6, 7, 8) filled with synthetic zeolite NaA, CaA, NaX. The ratio of layers CaA : NaX - 1 : 1. At the outlet of the adsorber hydrocarbon propellant contains: moisture - 0.0005 g/m3, sulfur compounds - 0,000053 g/m3(within 0.00001 wt.%).

The feed rate of the hydrocarbon mixture in the adsorber (6) - 0,0025 m/s at a pressure of 0.85 MPa and a temperature of 45oC. At the same time, the adsorber (7) operates in the regeneration mode, and the adsorber (8) in the cooling mode.

The obtained hydrocarbon propellant is cleared from the zeolite dust on the filters (9, 10) and sent (11) to the warehouse of finished products. According to its physico-chemical parameters obtained propellant corresponds to THE 39-892-93.

Regeneration and cooling of the adsorbent carried out in nitrogen with a residual oxygen content of not more than 2 vol.%. The flow of nitrogen initially passes adsorber (8) with svezheotremontirovannye zeolite and cools it to the 50oC, then the nitrogen undergoes heating in the oven to 320 - 350oC and fed into the adsorber (7) on the regeneration of the zeolite. When the article is perekluchaet on cooling.

Thus, the proposed method for hydrocarbon propellants allows you to:

to obtain a hydrocarbon propellants of high quality, which is fine purification from sulfur compounds (mass content of sulfur compounds in the final product does not exceed 0,00001%);

to expand the range of materials, using hydrocarbons containing C2-C7;

significantly reduce capital and operating costs due to the replacement of apparatus for obtaining the four individual hydrocarbons and host their mixing two apparatus to obtain a hydrocarbon mixture of a given composition, extension of service life of zeolites.

1. The method of obtaining hydrocarbon propellants, including rectification of hydrocarbons, cleaning, deodorization and drying, characterized in that the rectification process produce a mixture of hydrocarbons of a given composition with excess saturated vapour pressure corresponding to the excess pressure of saturated vapors of hydrocarbon propellants, and subjected to pre-cleaning and deodorization on charcoal and drying carried out on synthetic zeolites.

2. Str is the main raw material, cleaning and deodorization on synthetic zeolites with subsequent regeneration of the zeolites.

3. The method according to p. 1, characterized in that the drying, cleaning and deodorization is carried out by passing a mixture of hydrocarbons by placing successive layers of zeolite NaA, CaA and NaX.

4. The method according to p. 2, characterized in that the regeneration of zeolites provide nitrogen.

5. The method according to p. 2, characterized in that the regeneration is carried out dried and purified hydrocarbon gas.

 

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