Methanol processing method

FIELD: industrial organic synthesis and catalysts.

SUBSTANCE: invention provides a method for processing methanol into dimethyl ether and liquid hydrocarbons, the latter being used as high-octane components of gasolines Ai-92, 95. Processing comprises contacting of raw material, in at least one step, in at least one reactor containing catalyst: Pentasil-type zeolite and binder, followed by cooling resulting products, condensation and separation thereof to isolate methanol conversion hydrocarbon gases, water, and desired products, after which cooled hydrocarbon gases are recycled to methanol conversion stage in at least one reactor. Catalyst is characterized by SiO2/Al2O3 molar ratio 20-100, content of sodium oxide not higher than 0.2%, and additionally contained silicon dioxide and zirconium dioxide at following proportions of components: 1.0-15.0% silicon dioxide, 1.0-5.0% zirconium dioxide, 20-70% zeolite, and binder - the balance.

EFFECT: increased yield of desired products and improved performance characteristics of catalyst.

4 cl, 5 tbl, 18 ex

 

The invention relates to methods of processing of methanol used to produce liquid hydrocarbons and dimethyl ether. Such liquid hydrocarbons can be used as high-octane components of gasoline AI-92,95 with a low content of aromatics and benzene content not higher than 1%.

It is known that the selectivity of the conversion of methanol into valuable hydrocarbons and dimethyl ether (DME) is determined by the properties of the catalyst. Now for the conversion of methanol in liquid hydrocarbons and dimethyl ether using a catalytic system containing 65 wt.%. zeolite type pentasil H-ZSM-5, H-ZSM-11 or H-ZSM-4 and 35% wt. γ-Al2O3 [Proc. Int. Zeolite Conf, 6th. Meeting Date 1983, 316-324, 489-96: Guildford, UK. (English) 1984.

Known also numerous patent publications, declaring conditions for the conversion of methanol in liquid hydrocarbons. They can be divided into patents claiming the use of the proposed unmodified catalysts of pentelow (U.S. Patent No. 3931349), and pentelow subjected to the modification of the crystalline structure, for example the influence on the zeolite thermoprotei processing (TPO) at elevated temperatures of 500-600°and shielding the external surface of the crystals of the zeolite by impregnation with solutions of various substances or deposits of such substances from the gas phase (U.S. Patent No. A, 4392989 and the Russian Federation No. 218988, 2226544).

Known two-stage processing techniques of methanol in a fixed, fluidized and moving bed of the catalyst to produce liquid hydrocarbons (gasoline fractions), U.S. patent No. 3928483, 4543435 and one-step method for processing of methanol with obtaining DME (patent USSR No. 841578). Closer to the invention is a method of conversion of methanol, disclosed in U.S. patent No. 3928483, CL 10G 37/06, representing a two-stage process of methanol on the catalyst based on zeolite type pentelow ZSM-5, ZSM-11, ZSM-12 with the aim of obtaining DME and component of high-octane gasoline.

The disadvantage of this method is not sufficiently high yield of the target products.

Technical problem on which the invention is directed, is to increase the yield of the obtained product, the improvement of performance characteristics of the catalyst, namely the increase in mechanical strength of the granules of catalyst reduction, its degree of decontamination and the increase in the number of regeneration cycles at least 5-10 when meregenerasikan run of not less than 350 hours.

The technical result of the invention is to increase the yield of DME and high-octane components of motor fuels with a low content of aromatic hydrocarbons

The specified technical result is achieved by the described method of processing ODI of methanol by contacting the feedstock in at least one stage, in at least one reactor with a catalyst containing a zeolite of type pentasil and binder, cooling the products of condensation and separation of their emitting hydrocarbon gas reforming of methanol, water and target products and recycling the cooled hydrocarbon gas reforming of methanol in at least one reactor, which uses a catalyst containing a zeolite of type pentasil with a ratio of SiO2/Al2O3equal 25-100, containing not more than 0.2 wt.% sodium oxide, optionally containing silicon oxide and the oxides of zirconium in the following ratio, wt.%:

the silicon oxide1,0-15,0
the oxides of zirconium1,0-5,0
zeolite20-70
binderrest

Preferably cooled hydrocarbon gas is sent for recycling at a ratio of from 1 to 10 mole of gas per mole of methanol.

Preferably the process is carried out at a temperature of 250-450°and space velocity of the raw material is from 0.5 to 10 h-1.

It is preferable to use a catalyst with a zeolite-type pentasil who have undergone preliminary training includes treatment with sodium hydroxide solution, washing the zeolite from alkali, tinny exchange with receipt of NH 4-form of the zeolite.

Before using the catalyst, it is desirable to process steam or nitrogen, or mixtures thereof at a temperature of 450-800°C.

Increased efficiency of the used catalyst is explained, apparently, by modifying the acid properties and catalytic activity of the zeolite component in its special treatment, perhaps the promoting effect of the presence of oxides of zirconium, chosen experimentally and its quantitative content in the catalyst, which increases the mechanical strength of the granules and its ability to oxidative regeneration at a high yield of the products obtained when meregenerasikan run of not less than 350 hours.

The zeolites used in the composition of the proposed catalyst, are the domestic counterparts of pentelow computers, CVMS (both on THE 38.401528-85), WHC and PPM (on THE 38.102168-85), containing 0.2 to 0.5 mol.% Na2O and obtained by direct synthesis (WHC) or when exchanging the original Na-form of zeolite H - or NH4form.

As a binder component can be used synthetic silicates, aluminium oxide.

Below are examples of the preparation used in the proposed method, catalysts and examples that prove the effectiveness of the method with their use.

Example 1. Mix 160 g of aluminum hydroxide (Al with mass loss on ignition (PMP) 75 wt.%, 20 ml of Kremenets containing 250 g of silica in 1 liter and sodium in terms of oxide 5 g/l and 20 ml of an aqueous solution of nitrate Zirconia concentration in terms of zirconium dioxide equivalent of 250 g/l ZrO2the mixture is stirred, making it 50 g of anhydrous zeolite NCWM with kriminaalmenetlus module (KAM 34). The mixture was evaporated with stirring, ekstragiruyut and cut in the form of cylindrical pellets 3·3 mm. Pellets dried for 4-6 hours at a temperature of 80-110°C, calcined 6-8 hours at a maximum temperature of 550°C. Receive the catalyst composition, wt.%:

Zeolite50
ZrO25
SiO25
Aluminum oxide (OAl)rest

Example 2. Mix 240 g Al with the ingredients of example 1, taking a portion of the zeolite 30, carry out all the operations that were in example 1, and get the catalyst composition, wt.%:

Zeolite30
ZrO25
SiO25
OAlrest

Example 3. Perform all operations on the conditions of example 1, but take 280 g Al and 20 g of zeolite. After all the operations floor is given catalyst of the following composition, wt.%:

Zeolite20
ZrO25
SiO25
OAlrest

Example 4. Perform all operations as in example 1, but Al take 120 g and 60 g of zeolite After all operations have the catalyst composition, wt.%:

Zeolite60
ZrO25
SiO25
OAlrest

Example 5. 80 g Al and 70 g of zeolite molded with the rest of the ingredients in the conditions of example 1. Get a catalyst of the following composition, wt.%:

Zeolite70
ZrO25
SiO25
OAlrest

Example 6. 160 g Al and 50 g of anhydrous zeolite NCWM with CAM 18 formed in the conditions of example 1. The finished catalyst has the following composition, wt.%:

Zeolite50
ZrO25
SiO25
OAlrest

Example 7. In the conditions of example 1 are mixed with 160 g Al and 50 g of anhydrous zeolite NCWM with CAM 72. The finished catalyst has the following composition wt%:

Zeolite50
ZrO25
SiO25
OAlrest

Example 12. 144 g Al mixed with 28 ml of Kremenets in example 1, was added 28 ml of nitrate solution Zirconia or 15,18 g dihydrate nitrate Zirconia. For mixed weight add 50 g of anhydrous zeolite with the CAM 34. After all operations have the catalyst composition, wt.%:

Zeolite50
ZrO27
SiO27
OAlrest

Example 13. Perform all the operations of example 12, but instead of Kremenets add 20 ml of tetraethoxysilane. Get the catalyst of the same composition that given in example 12.

Example 14. 140 g Al mixed with 40 ml of Kremenets, with 50 g of anhydrous zeolite with CAM 34 and 25 ml of a solution of nitrate of Zirconia. After performing all the operations of example 1 are as catalyst of the following composition:

Zeolite50
ZrO2 5
SiO210
OAlrest

Example 15. The catalyst was formed in the conditions of example 14, but hanging Al is 120 g, and Kremenets take 60 ml of the Catalyst has a composition, wt.%:

Zeolite50
ZrO25
SiO215
OAlrest

Example 16. 192 g Al mixed with 4 ml of Kremenets and 4 ml of Zirconia, add 50 g of zeolite computers, as in example 1. After conducting standard transactions receive the catalyst composition, wt.%:

Zeolite50
ZrO21,0
SiO21,0
OAlrest

Samples of the catalysts were tested in the reaction of dehydration of methanol to dimethyl ether and obtaining liquid hydrocarbons (gasoline fractions) on running the install with catalyst loading of 20-50 cm3also on the installation of recycling the hydrocarbon gases. Below are the results of the tests.

Table 1 presents the results of the dehydration of methanol to DME on the catalysts with different content is of eulita and different molar ratio of SiO 2/Al2O3in the zeolite at 280°C, a pressure of 2 MPa, space velocity on methanol 1 h-1and duration of test 48 hours

From table 1 it is seen that high activity, providing the conversion of methanol, close to equilibrium, have samples of catalyst, containing 30-60 wt.% zeolite. At a lower content of zeolite in the catalyst (example 3) the degree of conversion of methanol decreases at higher (example 5) in the reaction products appear traces of hydrocarbons and reduced selectivity for dimethyl ether.

The change in the ratio of SiO2/Al2O3within wide limits /18-72/ no significant impact on the activity and selectivity of the catalyst.

Table 2 shows the results of experiments on dehydration of methanol to dimethyl ether in the catalysts with different content of silicon oxide. Conditions of the experiments: temperature 280°C, a pressure of 2 MPa, space velocity on methanol 1 h-1the duration of 250 hours

Table 2 shows that the high activity and stability have catalysts containing 5-10 wt.%. SiO2at low concentrations of SiO2(example 2) decreases the stability of the catalyst, as evidenced by the decrease in the conversion of methanol after 250 hours At bol is e high content (example 15) decreases the activity of the catalyst for conversion of methanol (79,5-80%), that is, apparently, the result of blocking the silicon oxide of the input Windows of the zeolite.

In table 3 the results of the dehydration of methanol to the catalyst of example 1 in the temperature range 280-350°and flow rate on liquid methanol 1-5 h-1. The experiments were conducted at a pressure of 2 MPa, the duration of the experiments 48 hours.

Table 3 Effect of dehydration on the activity and selectivity of the catalyst
The catalyst according to exampleConditions of experimentsThe conversion of methanol, %Selectivity for DME, %
Temperature, °Space velocity, h
1280182,0100
2300281,2100
3350579,698

From table 3 it is seen that the catalyst of the present invention has a high activity. When flow rate I h-1the catalyst provides the conversion of methanol, close to equilibrium already at 280°at flow rate 2 h-1to ensure the same transformation of the desired rise the temperature up to 300° And flow rate 5 h-1up to 350°C. However, a further rise in flow rate and temperature is not desirable, because already at 350°products of the reactions appear traces of hydrocarbons, which can lead to coking of the catalyst.

In table 4 the results of long-term experiments on dehydration of methanol on the catalysts prepared according to examples 1 and 14 of the present invention. The experiments were conducted under the conditions: temperature 280°C, a pressure of 2 MPa, space velocity on methanol 1 h-1.

Table 4. The stability of the catalysts according to the present invention
The catalyst according to exampleThe conversion of methanol, %
Hours of work, h
2505007501000
182,182,082,381,7
1481.482,282,581,3

As can be seen from table 4, samples of the catalyst of the present invention have a high activity, which does not decrease after 1000 hours of operation. Uploaded catalysts contained minor amounts of coke, which indicates the potential in the possibilities of a longer their operation.

Examples 17-18.

Conduct processing of methanol by contacting in two stages, in two reactors with a catalyst of the above composition, cooling the obtained products, condensation and separation of their emitting hydrocarbon gas reforming of methanol, water and target products and recycling the cooled hydrocarbon gas reforming of methanol in both reactors.

Example 17. Using the catalyst obtained in example 1. The process is carried out in the first reactor at a pressure of 2.0 MPa, a temperature of 360°s, the volumetric feed rate of the raw material 6,0 h-1and recycling of hydrocarbon gases 6 moles of gases on 1 mol of methanol, in the second reactor, the process is carried out at the same pressure, a temperature of 370°C, flow rate of feed of 2.0 h-1and recycling of hydrocarbon gases to 9.0 moles of gas per 1 mol of methanol. The result for 77.3 wt.% liquid hydrocarbons above C5,which was significantly higher similar (U.S. patent No. 3928483), the yield of liquid hydrocarbons above C5is 58,19% wt.

Table 5
The catalyst according to exampleThe selectivity of the formation of liquid hydrocarbons
On the original catalystAfter the first regenerationAfter the fifth is egenerali
177,376,475
477,277,075,8

Table 5 shows the results of tests of the catalysts in the two-stage scheme, as can be seen from the results, the catalysts have high selectivity with respect to outputs of liquid products, even after the fifth regeneration, and the operating time of the catalyst before regeneration was over 600 hours

Example 18. Using the catalyst of example 1. The process is carried out in the same reactor at a pressure of 2.0 MPa, a temperature of 340°C, space velocity of the raw material 6,0 h-1with recirculation neprevyshenie methanol conversion of methanol to DME is not less than 80 wt.% over 1000 hours before regeneration of the catalyst in comparison with the prior art (patent USSR No. 841578), where the operating time of the catalyst before regeneration does not exceed 500 hours.

1. The method of processing of methanol by contacting the feedstock in at least one stage, at least one reactor with a catalyst containing a zeolite type pentasil and binder, cooling the products of condensation and separation of their emitting hydrocarbon gas reforming of methanol, water and target products and recycling the cooled hydrocarbon gas reforming of methanol in at least one reactor, characterized in that use is utilizator, containing zeolite type pentasil a molar ratio of SiO2/Al2About3equal 25-100, containing not more than 0.2 wt.% sodium oxide, optionally containing silicon dioxide and zirconium oxide in the following ratio, wt.%:

silicon dioxide1,0-15,0
zirconium oxide1,0-5,0
zeolite20-70
binderrest

2. The method according to claim 1, characterized in that the cooled hydrocarbon gas is sent for recycling at a ratio of from 1 to 10 mole of gas per mole of methanol.

3. The method according to claim 1, characterized in that the process is carried out at a temperature of 250-450°and space velocity of the raw material is from 0.5 to 10 h-1.

4. The method according to claim 1, wherein the used catalyst with zeolite type pentasil who have undergone pre-treatment includes treatment with sodium hydroxide solution, washing the zeolite from alkali cation exchange with receipt of NH4zeolite.



 

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