The method of obtaining high-octane gasoline and aromatic hydrocarbons

 

(57) Abstract:

The invention relates to methods of producing aromatic hydrocarbons from hydrocarbons containing aliphatic olefins and paraffins C2-C12. The concentrate of aromatic hydrocarbons or gasoline enriched in aromatic hydrocarbons, get in contact feedstock at elevated temperature and pressure with a catalyst containing a group zeolite, zinc oxide, a mixture of oxides of two or more rare earth elements and boron oxide in the following ratio, wt.%: zeolite 50,0 - 70,0; zinc oxide 1,0 - 3,0; oxides of rare earth elements from 0.5 to 2.0; boron oxide 1,0 - 2,0, not exceeding 4,3% binder; the binder component is rest. The use of a catalyst of the composition in the process of aromatization increases the yield of aromatic hydrocarbons, the increase in selectivity to liquid products, and aromatic hydrocarbon, C6-C10. 3 table.

The invention relates to methods of producing aromatic hydrocarbons from hydrocarbons containing aliphatic hydrocarbon, C2-C12and can be used in the refining and petrochemical industry.

Using the catalyst composition of the zeolite group of pentelow ZSM-5, ZSM-11, DCM, CEC, WHC, etc. allows you to limit the composition of the products of hydrocarbon, C1-C12. The content of zeolite in the catalyst varies widely (from 1 to 99 wt.), and as the binder component typically use aluminum oxide, silicon oxide, aluminum silicates. The catalysts also contain metals or metal oxides (promoters) as components that increase their activity in the reaction of formation of aromatic hydrocarbons (aromatization). The content of the promoters in the catalyst generally is 0.1 to 10%

The most effective promoters of aromatization catalysts are zinc and gallium [1] Gallium, however, the metal is expensive and scarce, but the disadvantage of zinc-containing catalysts is reducing their activity as a result of ablation of zinc in the conditions of high temperature reaction and catalyst regeneration.

DL the deposits, rhenium or rare earth element (REE) [3]

In some cases, the presence of the second metal in the zinc-containing zeolite catalyst increases the yield of aromatic hydrocarbons in the conversion of gases. This effect was observed with the introduction of gallium [1] gold, platinum, silver [3] rhenium [4] it is also Known about the positive effect of REE on containing gallium zeolite catalyst for the aromatization of hydrocarbons, having in its composition paraffins C2C3and/or C4[5] With the introduction of a catalyst containing 0.2 to 1.0 wt. gallium, at least one of rare earth elements in an amount of 0.1 to 2.0 wt. there is an increase in the conversion of paraffins C2-C4and the selectivity of the process for aromatic hydrocarbons, and reduction of coke formation.

Closest to the proposed catalyst for aromatization of aliphatic hydrocarbons, C2-C12is the catalyst described in [3] Patented zeolite catalyst contains 0.1 to 10 wt. modifying metals zinc and metal from the following range: group IB and VIII of the Periodic system, germanium, rhenium, REE. The introduction of a second metal slows down the release of zinc from the catalyst.

The aim of the present invention is the creation of the Kie hydrocarbons, C2-C12with the use of a catalyst based on zeolite group of pentelow without expensive and scarce metals having high activity in the formation of aromatic hydrocarbons and high selectivity for liquid and aromatic hydrocarbon, C6-C9.

This objective is achieved in that used for the conversion of aliphatic hydrocarbons zeolite catalyst containing zinc is introduced a mixture of two or more oxides of rare-earth elements and boron oxide.

According to the invention the catalyst for obtaining aromatic hydrocarbons, and high-octane gasoline includes high-silica group zeolite, zinc oxide and rare-earth element, and is characterized by the fact that as a rare earth element catalyst contains a mixture of two or more oxides of rare earth elements, and optionally boron oxide in the following ratio, wt.

Zeolite 50,0 70,0

Zinc oxide 1,0 3,0

The sum of the REE oxides 0,5 2,0

The boron oxide 1,0 2,0, not more than 4.3 binder component

The Rest of the binder

Observe the technical effects of improving the yield of aromatic hydrocarbons in the process of aromatization aligations the increase of the yield of liquid hydrocarbons processing in a relatively harsh conditions of low-octane gasoline explains apparently, the stronger the promoting effect of several rare earth metals, and also the modifying influence of boron on the acid and the diffusion properties of the catalyst.

Used in the catalyst composition of the domestic high zeolites CVM and SVMS (TU 38.401528-85) in ion-exchange form, with the content of Na2O less than 0.2 wt. or WHC (TU 38.102168-85) have the following characteristics:

The molar ratio of SiO2/Al2O320 80

The content of Na2O, wt. Less than 0.2

The degree of crystallinity on ranganathaswamy analysis, Rel. Not less than 95

Static capacity heptane, cm3/g Not less than 0,20

As a binder component can be used synthetic aluminosilicates, silicon oxide, preferably aluminum oxide.

As a source of boron oxide B2O3use orthoboric acid, H3BO3. An aqueous solution of boric acid is introduced into the catalyst mass at the stage of mixing zeolite and a binder. In the preferred case, when used as a binder of aluminum oxide, an aqueous solution of boric acid is used for peptization of aluminum hydroxide.

Rare earth metals entering the Hor nitrates is introduced into the catalyst mass in the mixing process or impregnate them calcined molded catalyst.

Zinc is introduced into the zeolite in the ammonium exchanged form with aqueous solutions of zinc salts, such as chloride or nitrate, or by impregnation of the zeolite or catalyst solutions of zinc salts, or injected into the catalyst mass in the mixing process.

Introduction to the catalyst of zinc and REE by impregnation possible from a single solution containing both salts REE, and zinc salts, or two, containing only REE and only zinc. Before impregnation, the catalyst was subjected to heat or thermoprotei treatment at 400 to 600oC.

The catalysts according to the invention can be prepared in different ways and to different method of granulation of the zeolite with a binder, the method of introduction of the metal promoters in the catalyst or zeolite, etc. However, when the same method of preparation of the catalyst and with an equal amount of the promoting metals zinc and one of REE on the prototype, and zinc and mixtures of oxides of rare-earth elements, as well as a certain amount of boron oxide activity of the proposed catalysts in the formation of aromatic hydrocarbons, as well as the content of component C10+including naftalina above, and to obtain high-octane gasoline of low octane higher yield of liquid is ntake hydrocarbons, containing aliphatic olefins and paraffins C2-C12(low-octane gasoline fraction, a wide fraction of light hydrocarbons, refinery gases), with the proposed zeolite catalyst at elevated temperature and pressure can be carried out with circulation or non-circulation of hydrogen or hydrogen-containing gas or at least part neprevyshenie raw material or product.

Below are examples of the preparation of the catalysts according to the invention, and methods of their use for the preparation of aromatic hydrocarbons and high-octane gasoline or gasoline components.

Example 1. of 38.5 g of dry zeolite NH4CVMS (SiO2/Al2O321,5), obtained during exchange of the original Na+-form of zeolite CWMS OF 0.5 N ammonium nitrate solution containing 0.1 wt. Na2O, mixed with the 104.3 g of aluminum hydroxide (humidity 79,1%), pepsirefresh a solution of 2.3 g of H3BO3the mass of the evaporated and formed by extrusion. Catalyst pellet (diameter 3 mm, length 2 to 3 mm), dried, calcined at 550oC for 3 h, then treated with steam (flow rate of 0.5 g/SG catalyst) for 3 h at 500 550oC. the Cooled catalyst pellet fill in 70 ml of solution with240 50 wt. the amount of La2O3Pr2O3Nd2O360 45 wt.), incubated at room temperature for 2 h and evaporated. The catalyst was dried at 120oC and calcined at 550oC 3 o'clock

The resulting catalyst contains (wt.): zeolite 58,1; zinc oxide 1,6; REE oxides 1.1 boron oxide 1,5; boron oxide/aluminum oxide 0,040.

Example 2. of 38.5 g of dry zeolite NH4CVMS (SiO2/Al2O321,5) formed with 110,5 g of aluminum hydroxide pellets are dried, calcined at 550oC 3 h and treated with steam for 3 h at 500 550oC. the Cooled catalyst pellet fill in 70 ml of an aqueous solution containing 1.2 g of cerium nitrate Ce(NO3)3and 2,78 g Zn(NO3)2, incubated at room temperature for 2 h and evaporated, then dried and calcined at 550oC 3 o'clock

The resulting catalyst contains (wt.): zeolite 58,1; zinc oxide 1,6; CeO21,1.

Example 3. The catalyst prepared according to example 1, but the consumption of reagents is as follows:

Dry zeolite NH4CUMS, g 33,3

Aluminum hydroxide, g USD 128.0

Boric acid, g 1,9

The zinc nitrate Zn(NO3)2, g 4,2

Concentrate salts REE, ml 1,5

The calcined catalyst contains (wt.SUB>2O30,040.

Example 4. The catalyst prepared according to example 1 with the following changes: zeolite NH4Computers, SiO2/Al2O339,3; the content of Na2O less than 0.02 wt. salt solution REE contains equimolar mixture of nitrates of lanthanum and cerium, the concentration of 150 g/l; catalyst prior to impregnation with a solution of zinc salts and REE are steamed not.

The consumption of reagents is as follows:

Dry zeolite NH4The CVM, g 33,3

Aluminum hydroxide, g 133,5

Boric acid, g 2,1

Nitrate zinc, g 1,4

The solution of the nitrates of rare-earth elements (lanthanum and cerium), ml 3.9 to

The calcined catalyst contains (wt.): zeolite 50,0; zinc oxide 1,0; oxides of rare-earth elements (lanthanum and cerium) 0,5; boron oxide 2,0; B2O3/Al2O30,043.

Example 5. The catalyst prepared according to example 4, using zeolite WHC (SiO2/Al2O380,0), obtained with a content of Na2O 0.1 wt. calcined at 400 550oC 5 o'clock the Consumption of reagents is as follows:

Zeolite WHC, g 42,0

Aluminum hydroxide, g 78,9

Boric acid, g 1,1

Nitrate zinc, g 1,4

The solution of the nitrates of rare-earth elements (lanthanum and cerium), ml 3.9 to

The calcined catalyst contains (wt.): zeolite 70,0; zinc oxide 1,0; oxides of rare-earth elements (lanthanum and cerium) 0,5; boron oxide to 1.0; B2O3oC 3 h and maintained at 550oC in a stream of nitrogen.

The catalyst contains (wt.): zeolite 65,0; zinc oxide 1,5; oxides of rare-earth elements (cerium, lanthanum, neodymium, praseodymium) 2,0; boron oxide to 1.0; B2O3/Al2O30,033.

Example 7. The catalyst prepared according to example 6, but using calcined zeolite DCM containing 0.8 wt. zinc obtained by the exchange of NH4The CVM with 0.4 N solution of zinc chloride.

The consumption of reagents is as follows:

Zn CC, g 39,0

Aluminum hydroxide, g 88,0

Boric acid, g 1,1

Nitrate zinc, g 1,9

Concentrate salts REE, ml 6

The calcined catalyst contains (wt.): zeolite 64,4; zinc oxide 2,0; oxides of rare-earth elements (cerium, lanthanum, neodymium, praseodymium) 2,0; boron oxide to 1.0; B2O3/Al2O30,033.

In table. 1 shows the composition of the catalysts (wt.), prepared in accordance with the invention of examples 1 and 3-7, and in accordance with the prototype according to example 2.

Primarycolour on running the install with catalyst loading of 20 ml. The composition of raw materials are given in table.2. Products from gasoline fractions collected within 24 h, and gas fractions for 3 h, then chromatographically determined their composition.

Data conversion of various feedstocks containing aliphatic hydrocarbon, C2-C12presented in table.3.

Comparison of transformation of the same types of raw materials on the catalyst according to the alleged invention (examples 8-10) and the prototype (examples 11-13) indicates an increase in activity and selectivity in the formation of aromatic hydrocarbons, C6-C10zeolite catalyst containing boron oxide and a mixture of oxides of rare-earth elements. This effect is more pronounced at high temperature conversion of light materials.

The method of obtaining high-octane gasoline and aromatic hydrocarbons by contact of hydrocarbons containing aliphatic olefins and paraffins WITH2WITH12at elevated temperature and pressure with a catalyst containing a group zeolite, zinc oxide, rare earth element and a binder component, wherein the catalyst as a rare earth element contains a mixture of oxides of two or more rare earth e,0

Zinc oxide 1,0 3,0

The oxide of rare earth elements 0,5 2,0

The boron oxide 1,0 2,0, not more than 4.3% of the binder component

The Rest of the binder component

 

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