JPS5929635B2 - Method for producing fuel oil composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a fuel oil composition from a lower-hydric alcohol having 1 to 3 carbon atoms and imbutylene.

In recent years, lead pollution in exhaust gas from internal combustion engines has become a problem, and regular gasoline has already been completely lead-free.
Premium gasoline is also expected to become unleaded someday.

Therefore, in order to make the base gasoline unleaded without changing the mixing ratio too much and to maintain the octane number at 2, it is necessary to add an octane number improver.

There are many compounds known as octane improvers.

Among them, ethers having a branched alkyl group were introduced at the Third World Petroleum Congress.
oleum Congress, Sec ■, 397
(1951), for example methyl tert-butyl ether (MTBE),
It is known that crt-phthyl ether and isopropyl tcrt-butyl ether have extremely high octane numbers.

For example, a method for producing MTBE is known in which methanol and imbutylene are reacted in the presence of an acid catalyst.

In particular, several methods using strong acid type cation conversion resins as catalysts have been proposed (for example, Japanese Patent Publication No. 48-3480).
3, Publication 49-61109. Publication 50-58006. U
S2.480,940, etc.).

However, in these conventional methods, acidic substances are extracted from the strongly acidic cation exchange resin during the reaction and are entrained in the reaction product mixture. Does the reverse reaction of MTBE occur considerably because it has a tertiary carbon atom? This causes the inconvenient phenomenon of decomposition into methanol and isobutylene.
This will reduce the yield of MTBE.

Furthermore, fuel oil containing such acidic substances cannot be mixed directly into fuel oil.

The present inventors removed such undesirable acidic substances from the reaction product mixture using a solid particulate acid neutralizer, and then carried out a flushing operation and a distillation operation to continuously produce lower-hydric alcohols and tertiary olefins. He invented a process for industrially producing tertiary alkyl ethers with good yield and filed a separate patent application.

The present invention relates to a method for producing a fuel oil composition from a lower-hydric alcohol having 1 to 3 carbon atoms and isobutylene.

In other words, a lower alcohol having 1 to 3 carbon atoms and imbutylene are combined with a lower alcohol: isobutylene-1.
: A fixed bed filled with strong acid type cation exchange resin particles with an average particle size of 0.2 to 10 mm at a molar ratio of 1 to 40 was heated at a temperature of O to 10.
0°C, liquid space velocity 0.1-50 (1/hr),
The lower-hydric alcohol and isobutylene are reacted by continuous passage at pressures between 1 and 50 degrees, and the reaction mixture is divided into two streams, one stream having an average particle size of 0.
The former flow is passed through a fixed bed filled with 1 to 10 g of a water-insoluble solid granular acid neutralizer at a temperature of 0 to 100°C, and the other stream is circulated and fed to the fixed bed filled with the ion exchange resin. Production of a fuel oil composition by flushing out unreacted isobutylene by introducing a stream of the reaction mixture into a flash column and blending 2 to 30 volumes of the reaction product obtained from the bottom of the column with fuel for internal combustion engines. It is about the method.

In the second aspect of the present invention, lower-hydric alcohol and imbutylene are used as raw materials.

Commercially available lower-hydric alcohols containing 1 to 3 carbon atoms (methyl alcohol, ethyl alcohol, n-propyl alcohol, 1so-propyl alcohol) can be used, but those with a water content of about 1 wt% or less It is preferable to use

Further, isobutylene is preferably a high-purity product, but a hydrocarbon mixture containing isobutylene may be used.

That is, the mixture may contain n-butane, isobutane, butene-1, butene-2, butadiene, etc. in addition to isobutylene.

The lower-hydric alcohol and imbutylene, either separately or in a mixture, are heated to a temperature near the reaction temperature and introduced into a catalyst bed of a strong acid type cation exchange resin.

The molar ratio of lower-hydric alcohol and isobutylene to be supplied is lower-hydric alcohol:isobutylene=1:1 to 4.

Preferably it is 1:1 to 2.5. If the amount is less than (2), the amount of unreacted lower-hydric alcohol increases and a step for separating the unreacted alcohol becomes necessary.

In other words, the number of moles of inbutylene is larger than that of lower-hydric alcohol, and the content of unreacted lower-hydric alcohol in the reaction product is minimized, thereby eliminating the separation step for unreacted lower-hydric alcohol. This is a feature of the present invention.

Moreover, if it is more than 4, the amount of unreacted isobutylene will increase, which will put an extra burden on the subsequent unreacted gas separation step, which is inconvenient, and the production of low molecular weight polymers of inbutylene will increase as a side reaction.

The strong acid type cation exchange resin as used in the present invention is a cation exchange resin exhibiting strong acidity, and representative examples thereof include styrene sulfonic acid type resin and phenol sulfonic acid type resin.

A styrene-based sulfonic acid type ion exchange resin is a sulfonated resin obtained by copolymerizing styrene and a polyunsaturated compound such as divinylbenzene, and is generally represented by the following formula.

Furthermore, the phenolsulfonic acid type resin is usually obtained by condensing phenolsulfonic acid with formaldehyde, and is usually represented by the following formula.

The above-mentioned strong acid type cation exchange resin is used as a catalyst in the present invention, and is used in the form of spherical or cylindrical particles having an average particle size of 0.2 to LOrnrn.

The catalyst particles are packed into a pressure-resistant circular reaction vessel to form a fixed bed.

The size of the fixed bed is not particularly limited.

Usually the height is 0.2m to 20m.

A plurality of fixed beds can be used in series or in parallel.

The aforementioned lower-hydric alcohol and imbutylene are continuously fed from the upper or lower end of the fixed bed, preferably from the upper end.

The supply amount is determined by the liquid hourly space velocity of o, il 5 (1/ h r
).

The liquid hourly space velocity referred to here is measured at 20°C and 2.5 kg/i per hour (hr) per 177 I'' of catalyst.
The newly supplied lower-hydric alcohol S and the newly supplied 2
and the total volume (m3) of isobutylene recovered and supplied from the unreacted gas separation step described below.

If the feed rate of the reactant (raw material) is less than 0.1 (1/hr), the reaction will proceed satisfactorily, but the amount of the main product obtained will be small, which is not only industrially disadvantageous, but also Decomposition of objects increases.

Moreover, if the supply amount is less than 50 (1/hr), the reaction will not be sufficiently achieved and the burden of the subsequent purification process will be heavy, which is disadvantageous.

An inert solvent can also be used in the reaction; for example, the bucum-butene fraction produced during naphtha decomposition can be used as it is as an inbutylene raw material.

In the third aspect of the present invention, when lower-hydric alcohol and imbutylene are passed through a fixed bed, the reaction mixture passing through the fixed bed is divided into two streams, and one stream is followed by a fixed bed filled with an acid neutralizing agent. A method is employed in which the ion exchange resin is supplied to the bed and the other stream is directly circulated to the fixed bed packed with the ion exchange resin.

In this case, the amount of combined flow is preferably 3 to 15 (by weight) of the latter (circulating amount) relative to the former amount of 1.

In this case, S is 3, and the liquid hourly space velocity, which indicates the amount of raw material supplied, is not related to the amount of reaction mixture directly circulated to the reactor as described above.

The reason why this circulating supply system is adopted in the present invention is as follows.

In other words, the reaction between the lower-hydric alcohol and imbutylene in the third aspect of the present invention is an exothermic reaction, and due to the liquid quality of the catalyst used in the present invention, the temperature inside the reactor must be kept constant, and high temperatures cannot be avoided. This must be strictly avoided in terms of suppressing side reactions and deteriorating the catalyst.

If a circulation system is not used, the temperature difference between the outlet and inlet of the reactor will be very large, and a special cooler or the like must be installed inside the reactor.

Moreover, even in this case, the presence of localized high-temperature parts often occurs, which is disadvantageous.

In the case of a circulation system, the temperature within the reaction bed is maintained sufficiently uniform.

The reaction pressure of the present invention is 1 to 50 atm, preferably 5 to 30 atm.
There is an atm"Q.

If the reaction pressure is lower than latm, the reaction will not be sufficiently achieved, and if it is higher than 50 atm, the reaction vessel 2 and its attached equipment must be made to be durable, which is industrially disadvantageous.

In the second aspect of the present invention, the reaction temperature is 0°C to 100°C.

If the reaction temperature is lower than 0°C, the reaction will not proceed sufficiently.

Further, if the temperature is higher than 100°C, side reactions such as oligomerization reaction of inbutylene will increase, which is not preferable.

Preferably the temperature is above 30°C and up to 60°C.

Generally, the higher the reaction temperature, the more acidic substances flow out from the strongly acidic cation exchange resin used as a catalyst, and the faster the catalyst deteriorates.

In addition, even if the reaction temperature is low, a small amount of strongly acidic substances are continuously extracted from the strong acid type cation exchange resin into the reaction mixture and flow out in a mixed state with the reaction mixture. An inconvenient phenomenon is observed.

In this way, when the reaction mixture mixed with an acidic substance is directly fed to the subsequent unreacted gas separation step and the unreacted gas is flushed (flashing operation usually involves heating), the main product is Decomposition (reverse reaction) is caused, reducing the yield, and furthermore, corrosion occurs in various parts of the equipment.

Furthermore, it is extremely undesirable to mix acidic substances into fuel oil in terms of the properties of the fuel.

In order to remove these strongly acidic substances, it is usually possible to neutralize them by adding strongly basic substances such as caustic soda, calcium oxide or hydroxide to water, but in that case, neutralization is necessary. It is difficult to separate the salts produced in the reaction, and the concentration of acidic substances flowing out varies relatively greatly depending on changes in the type of catalyst, reaction temperature, flow rate of raw materials, reaction time, etc. It is difficult to control the amount.

If the amount of base is small, acidic substances may not be completely removed;
If the above-mentioned disadvantages still remain and are too large, the subsequent unreacted gas separation step must be carried out under conditions dealing with strongly alkaline lJi materials, and the product must therefore be washed and distilled before being mixed into the fuel for internal combustion engines. This is extremely inconvenient as it requires the following operations.

Furthermore, when solids such as the above-mentioned caustic soda and calcium oxide are used as they are, these solids dissolve out during continuous use, resulting in the same inconvenience as described above.

Also, it may be possible to remove the acidic substances that flow out using an adsorbent such as activated carbon, but the adsorption capacity is small, and if the concentration of the acid to be adsorbed decreases, the acid adsorption ability will decrease significantly. .

According to the third aspect of the present invention, in order to solve such problems and to react a lower-hydric alcohol and isobutylene in a very effective and continuous manner, the reaction mixture is first treated with an average particle size of 01 to 0.
One of the characteristics is that the mixture is passed through a fixed bed filled with 10 mm of water-insoluble solid particulate acid neutralizer to bring them into contact.

By doing so, the above-mentioned disadvantages are eliminated.

The water-insoluble solid particulate acid neutralizer here has extremely low solubility in water (the solubility in water is 0.1 (,9/10CB9 water) or less under normal usage conditions).
, and is usually an inorganic solid particulate material having acid neutralization active sites of 1.0 (m mode/ 9 ) or more.

Here, the acid neutralization active site is obtained by adding the solid substance to a 1 wt% H2SO4 aqueous solution, leaving it to stand at 50°C for 10 hours, and then removing the vaginal solid substance and removing H2SO4 in the remaining aqueous solution. It is determined by converting the number of millimoles (mmode) per gram of the solid substance.

The water-insoluble solid particulate acid neutralizer used in the present invention is usually M, ? oxide, Al oxide, Mg and A6 double oxide and their hydrates, MgU and or A6 and Na,
and at least one element selected from C, Si, Ca, Ba, Sr, etc., S and their hydrates, etc., such as M,! 70M90-mH20
(However, m = 0 to 0.5), Ag203, Baytrota/L/Site (6Mgo・Ag2O3・C02・
12H20), Ad203 ・m5i02 ・nH2O
, (m=0, 5-3, n-1-6), A62031 n
H2022,5MgO-Ag203'nH2O,Na2
O-A7203-n H20,2Mgo・6SiO2・
nH2O (all n=1 to 6), etc. are used.

Among these, hydrotalcite 2 and M,? 0 is preferably used in the present invention.

Hydrotalcite usually has a molar ratio of magnesium to aluminum of about 3, but when it is synthesized, it can be synthesized with a molar ratio over a wide range.

However, even if the molar ratio of magnesium to aluminum is 2 in the range of 1 to 10, the X-ray diffraction diagram may show a characteristic peak of hydrocrusite, where the molar ratio of magnesium to aluminum is 3. Those having an aluminum molar ratio of 1 to 10 are also included in the hydrocrusite referred to in the present invention and can be effectively used according to the present invention.

In the second aspect of the present invention, the solid particulate acid neutralizer is used as a fixed bed packed in a container in the form of spheres, flakes or cylinders having an average particle size of 0.1 to LOmrn.

The reaction mixture is passed continuously through this fixed bed at a temperature of 0 to 100°C.

If the temperature is lower than 0°C, not only the acidic substance cannot be removed sufficiently, but also the reaction mixture discharged from the reactor must be cooled, which is disadvantageous because heat loss occurs.

Temperatures higher than 100° C. are disadvantageous because the reaction mixture exiting the reactor must be heated, resulting in heat loss.

Preferably, the temperature may be around the reaction temperature.

That is, it is sufficient to flow the reaction mixture into the neutralizer packed bed in a natural number of pipes from the reactor outlet to the neutralizer packed bed inlet.

Further, the amount of the reaction mixture passed through the fixed bed is usually 0,i~20 (1/hr) in terms of liquid hourly space velocity.

In accordance with the present invention, the reaction mixture is then introduced into a flash tower to perform a flashing operation.

A flash tower is usually a multi-stage tower, and light compounds, mainly unreacted inbutylene, are flashed and separated from the top of the tower.

Two to three flash towers can be used in multiple stages in series.

The separated imbutylene can also be liquefied and recycled to the initial reactor.

The liquid fluid obtained from the bottom of the flash tower is the reaction product of lower-hydric alcohols and imbutylene.

The process of the present invention is accomplished by adding 2 to 30% by volume of the reaction product obtained from the bottom of the flash tower to various internal combustion engine fuels.

A major feature of the present invention is that a fuel oil composition can be obtained by directly mixing the liquid fluid obtained from the flash tower with fuel oil.

The mixing method is not particularly limited, and it is sufficient to simply mix the two.

As fuel for internal combustion engines, various fractions obtained by distilling synthetic or natural petroleum, and various hydrocarbon fuels obtained by decomposing and reforming these fractions are used.

In particular, by mixing 2 to 30% by volume with motor gasoline, a fuel oil composition can be obtained which produces exhaust gas with increased octane number and reduced concentration of nitrogen oxides.

As the base gasoline, for example, straight-run gasoline, cracked gasoline, catalytically cracked gasoline, catalytically reformed gasoline, etc. are used, and these gasoline base materials can be used alone or as a mixture.

It is also possible to further mix in additives that are conventionally added to fuel oils.

Next, in order to explain the method of the present invention more specifically, an example of the process will be explained with reference to the drawings.

In Figure 3, the raw material lower-hydric alcohol passes through pipe 1.
Raw material isobutylene is fed through pipe line 2.

If necessary, recovered unreacted inbutylene, which will be described later, is combined with fresh isobutylene fed from pipe 2 via pipe 9 to be recycled and used.

The two raw materials are mixed through pipe 4, further through pipe 5, heated in heat exchanger E-1, and maintained at a predetermined reaction temperature.
It enters a fixed bed reaction column D-1 filled with strong acid type cation exchange resin particles.

The fluid exiting the reaction tower D-1 is divided into two streams, one stream is circulated by a circulation pump P and is circulated to the reaction tower D-1 via a pipe 6 either as it is or combined with new raw material, The other stream enters via line 7 neutralization column D-2, which is a fixed bed filled with solid particulate acid neutralizer insoluble in water.

The pressure around the reaction column D-1g and the neutralization column D-2 is controlled to a predetermined pressure by a pressure control valve PC■.

The fluid leaving the neutralization tower R12 passes through the pipe 8 to the flash tower D.
Enter -3.

The fluid entering the flash tower is connected to the pressure control valve PC.
The pressure is reduced by V and the temperature is controlled by heat exchanger E-2.

A gaseous fluid containing unreacted imbutylene is discharged from the top of the flash tower T)-3 through pipe 9, and if it is to be reused in the reaction, it is liquefied and then transferred to pipe 2 for raw material imbutylene as described above. join together.

The liquid fluid flowing out from the bottom of the flash tower D-3 through line 10 is transferred from the base gasoline tank through line 11, or is mixed with solin in a predetermined ratio.

Next, the features of the present invention will be described in more detail with reference to some examples.

Example 1 A styrene-type ion exchange resin (Amberlyst-15 manufactured by Rohm and Haas, average particle size 0.5) was placed in the reaction column D-'l.
mmφ) catalyst 306 and hydrotalcite (6Mgo・Al2O2・CO2・12H20,
Filled with 20e (average particle size 0.7 mmφ).

58.5 kg of methanol (99% purity) via pipe 1
/hr (1,83 kgmo6e/hr).

On the other hand, inbutylene (purity 99%) is supplied via pipe 2.
28.3 at a flow rate of O5, O kg/hr and via line 9 to circulate and reuse unreacted isobutylene.
Since it is fed at a flow rate of kg/hr, the flow rate of isobutylene in pipe 3 is 133.3 kg/hr (2,
38 kg mode/hr).

The liquid hourly space velocity of the raw material is 10 (1/hr).

The pressure inside the reaction system is 15kg/Cr due to PCV operation.
Retained by LG.

The mixed raw materials imbutylene and methanol are circulated through the circulation pipe 6
It merges with the fluid that has flowed through the pipe 5 and flows into the reaction tower D.
-1.

The inlet temperature of the reaction column D-1 is controlled by the heat exchanger E-1 to be 50'C, and the flow rate of the fluid in the pipe 6 is 7 times the flow rate of the raw material charged in the pipe S. It is controlled by the circulation pump P so that

The flow rate of the fluid leaving the reaction column D-1 and passing through the pipe γ is 1
91.8 kg/hr, and the composition of the reaction product is 8
5.2wt% Unreacted inbutylene composition is 14.8wt%
, unreacted methanol is o%, and the acid concentration of this fluid is 3.5×10″4 eq/lJ.

The fluid that has passed through the neutralization tower D-2 via the pipe γ passes through the pipe 8 and then enters the flash tower D-3 above and below the palm.

3 unreacted isobutylene from the top of flash tower D-3
Line 9 was flushed with a flow rate of 1.8 kg/hr.
The raw material is then joined to the imbutylene line.

The reaction product is 160ky from the bottom of flash tower D-3.
It is extracted at a flow rate of /hr.

The acid concentration of this liquid fluid is extremely low at 1.4×10 −7 eq/l.

Regular gasoline 19 is added to this liquid fluid through pipe 11.
By mixing at a flow rate of 261/hr, a fuel oil composition containing 10 parts by volume of the reaction product is obtained.

The research octane number of this fuel oil was 95.

Example 2 30 g of a sulfonated resin obtained by polymerizing styrene containing about 14% divinylbenzene and having a particle size of about 20 to 50 mesh was used as a catalyst to be packed in the reaction column D-1, and 1 and methanol (purity 99)
36.3 kg/hr (1,14kgmoge/
hr) and isobutylene (99% purity) via lines 2S and 9 at flow rates of 70.1 kg/hr and 44.4 kg/hr, therefore line 3
The total amount of inbutylene is 114.5 kg/hr (
The flow rate is 2,04 kgmo6e/hr).

The liquid hourly space velocity is 8 (1/hr). Heat exchanger E-1 is controlled so that the inlet temperature of reaction column D-1 is 40°C.

Other than the above, this embodiment is the same as the first embodiment.

From the bottom of flash tower D-3, the reaction product or IO4,
It was extracted at a flow rate of 3 kg/hr, and the acid concentration was 1. I
It has an extremely low concentration of X I F7e q/ll.

Regular gasoline is added to this liquid fluid through pipe 11.
The reaction product 15 was mixed at a flow rate of 6 l/hr.
A fuel oil composition containing % by volume is obtained.

The research octane rating for this fuel was 96.

Example 3 A styrene-type cation exchange resin (Amberlite IR manufactured by Rohm & Birth Co., Ltd.) was used as a catalyst to be filled in the reaction column D-1.
-121 replaced with H+, particle size 0.6 mmφ) 3
Using 1f, add 32% isopropyl alcohol via pipe 1.
．． 1 kg/hr (0,54kgmo(le/h
r), the C4 fraction containing 40% of inbutylene was passed through line 2 at a flow rate of 82.2 kg/hr (0.0% of inbutylene).
The reaction was carried out in the same manner as in Example 1, using a flow rate of 59 kg mode/hr) and a liquid hourly space velocity of 6 (x/hr).

From the top of Flash Tower D-3, the isobutylene content was 5.
2% unreacted gas is discharged at a flow rate of 51.9 kg/hr, and the reaction product is discharged from the bottom of the column at a flow rate of 61.81 y/hr.
The acid concentration of this liquid fluid is 1.1X1.
It has an extremely low concentration of 0-7 etq.

Regular gasoline is added to this liquid fluid through pipe 11.
A fuel oil composition containing 15% by volume of this reaction product is obtained by mixing with 11 J/hr of fluid.

The research octane number of this fuel oil was 96.

[Brief explanation of the drawing]

The figure is a schematic system diagram illustrating an example of the method of the present invention. D-1... Reaction tower, D-2... Neutralization tower, PCV... Kingka control valve, P...
...Circulation pump, D-3...Flash tower.

Claims (1)

[Scope of Claims] 1 Lower-hydric alcohol having 1 to 3 carbon atoms and isobutylene, lower-hydric alcohol:isobutylene-1:1~
A fixed bed filled with strong acid type cation conversion resin particles with an average particle size of 0.2 to Lomm at a molar ratio of
Reacting the lower-hydric alcohol and imbutylene by continuous passage at a liquid hourly space velocity of 0.1 to 50 (1/hr) and an upward flow of 1 to 50 °C, dividing the reaction mixture into two streams, One stream is passed through a fixed bed packed with a water-insoluble solid particulate acid neutralizer with an average particle size of 0.1 to 10 mm at a temperature of 0 to 100°C, and the other stream is passed through a fixed bed packed with the ion exchange resin. The amount of the divided stream is 1 to 15% by weight of the former, and the reaction mixture of the former stream is introduced into a flash column to remove unreacted inorganic acid. butylene is removed by flushing,
The reaction product obtained from the bottom of the tower is used as fuel for internal combustion engines.
A method for producing a fuel oil composition by zero volume mixing. 2. Claim 1, characterized in that hydrotalcite, magnesium oxide, alumina, silica S, and a double salt containing magnesium oxide, alumina, and silica are used as the water-insoluble solid particulate acid neutralizer. A method for producing a fuel oil composition.