KR102047139B1 - Method and apparatus for producing paraffin - Google Patents

Abstract

A method for producing paraffins is disclosed by a reduction reaction which proceeds in the presence of a reducing catalyst from olefins and hydrogen in a gaseous state. In this method, a plurality of catalyst tanks 3 and 4 each filled with the reduction catalyst are provided in series along the mainstream lines 21, 24, and 26 through which hydrogen flows. The olefin is divided and added to the mainstream lines 21 and 24 so that the molar amount of hydrogen in the introduction gas G1 and G3 into the catalyst tanks 3 and 4 becomes larger than the molar amount of the olefin.

Description

Paraffin manufacturing method and manufacturing apparatus {METHOD AND APPARATUS FOR PRODUCING PARAFFIN}

The present invention relates to a method and apparatus for producing paraffins such as ethane and propane from olefins such as ethylene and propylene.

Ethane and propane in paraffins (saturated chain hydrocarbons) are obtained by fractionating petroleum. Ethane is used not only as a raw material of ethylene and chloroethylene, but also as a cryogenic cooling material. On the other hand, propane is often used as an LPG as a gas fuel, but recently, it is used in the field of electronic materials such as semiconductors, and for this purpose, propane of high purity is particularly required. For example, the concentration of each impurity in high purity propane is required to be less than 1 ppm.

It is possible to produce paraffin such as ethane or propane of high purity by precise distillation at the stage of cracking crude oil and performing fractionation. However, precise distillation conditions need to be set, resulting in an increase in cost. On the other hand, ethane is a raw material for petroleum products, such as ethylene and chloroethylene, and propane is mainly used as a gas fuel, and high purity ethane and propane are not needed for such use. Therefore, due to high-purity paraffin with little demand, purification without profitability such as precise distillation at refineries as an industrial product is not performed.

The raw material gas containing propane used as a high purity raw material as a main component includes methane, ethane, propylene, isobutane and normal butane (n-butane), for example, but the high purity is achieved by removing these impurities. The method of making is already known (for example, refer patent document 1 and 2).

Patent Literature 1 proposes a technique for recovering high-purity propane from low-purity propane by adsorbing and removing ethane, propylene, isobutane, normal butane, and the like prior to propane, using a molecular sieve or activated carbon as an adsorbent. Patent Document 2 proposes a method for purifying paraffin (including propane) from a raw material containing paraffin (including propane) having 2 to 6 carbon atoms and olefin (including propylene) having 2 to 6 carbon atoms, A technique for recovering and purifying paraffin that has not been absorbed into the absorbent liquid while preferentially absorbing the olefin into the absorbent liquid containing silver ions has been proposed. In the methods of Patent Literatures 1 and 2, both of the propanes are removed by performing the adsorption operation or the absorption operation, and part of the propane is lost together with the impurity, so it is not possible to recover the propane at a high recovery rate.

On the other hand, in patent document 3, the technique of manufacturing propane by adding hydrogen to liquid propylene by reaction operation is proposed, and the fall of a recovery rate does not occur. However, since the temperature rises due to the exothermic reaction, the reaction operation cannot be performed in the high concentration of propylene, and the concentration is 25%. In addition, two tanks filled with a nickel catalyst are used, but one of them is a catalyst exchange or a preliminary container for regeneration, and propane reaction of propylene is substantially carried out in one tank of catalyst. .

JP 2012-25729 A WO 2010074019 A US 3509226 A

It is an object of the present invention to provide a method and apparatus capable of substantially completely paraffinizing when paraffin is prepared by reducing high concentrations of olefins with hydrogen.

According to a first aspect of the present invention, there is provided a method for producing paraffin from a olefin and hydrogen in a gaseous state by a reduction reaction proceeding in the presence of a reducing catalyst, wherein a plurality of catalyst tanks each filled with the reducing catalyst are hydrogen. The olefin is divided with respect to the liquor line so that the molar amount of hydrogen introduced into each of the catalyst tanks in the gaseous state is greater than the molar amount of olefins introduced into each of the catalyst baths in the gaseous state. There is provided a method for producing paraffin, which is added.

When the olefin is reduced with hydrogen, the temperature rises because it is an exothermic reaction. For example, in the case of ethylene and in the case of propylene, the reaction is exothermic reaction as follows (in the formula below, ΔH represents a change in enthalpy, and a minus sign indicates that the enthalpy decreases and generates heat as a result of the reaction. ).

Therefore, if this reaction is performed with the liquid pure olefin, since the molecules of the olefin are approaching each other, the calorific value per unit volume of the olefin increases, and the exothermic reaction occurs at a large rate so that the cooling rate does not stick. As a result, in the prior art, 25% of the concentration was limited as the liquid olefin as the raw material as in Patent Document 3. In order to solve this problem, in the present invention, the intermolecular distance is increased by the reaction in the gas phase, the reaction amount per unit volume of the olefin is reduced, and the calorific value is reduced. For example, the mass per mole of propylene is 42.08 g from the molecular weight, and the number of molecules is 6 × 10 ²³ in Avogadro's number. Since the specific gravity of the liquid is 0.6139 g / cm 3, the space occupied by one molecule in the liquid phase is 11.42 × 10 ⁻²³ cm 3. On the other hand, in the gas phase, the volume occupied by one mole at 1 atm and 0 ° C. is 22.4 dm ³ , so the space occupied by one molecule is 3.733 × 10 ⁻²⁰ cm 3. Therefore, when the liquid phase from the gas phase, the distance between molecules is about 330 times the space occupied by one molecule, so the distance between molecules can be said to be 6.9 times longer. Accordingly, the reduction reaction of propylene is an exothermic reaction, and the longer the intermolecular distance, the easier the heat dissipation and heat removal by heat transfer. Therefore, the reduction reaction is better performed in the gas phase.

In addition, in this method, a catalyst tank is divided into at least two tanks or more in series, and olefin is divided and added to each catalyst tank using hydrogen as a mainstream. Reduction of olefins with hydrogen is more likely to proceed by adding more hydrogen than the theoretical equivalent. Therefore, by dividing the catalyst tank into two or more tanks in series and dividingly adding olefin (ethylene or propylene) with hydrogen as the mainstream, the amount of hydrogen / olefin amount (molar ratio) in each catalyst tank can be made larger. , The reduction reaction can be promoted. In addition, since olefin (ethylene or propylene) is added in two or more divisions, the increase in reaction temperature per catalyst tank can be reduced. The hydrogen purity of the liquor here is 99-99.99999 mol%, Preferably it is 99.999 mol% or more.

In a preferred embodiment, the molar amount of hydrogen and the molar amount of olefins introduced into the respective catalyst tanks are adjusted so that the hydrogen / olefin (molar ratio) is 1.1 or more.

In a preferred embodiment, the molar amount of olefins introduced into each of the plurality of catalyst tanks is equal.

When the amount of olefins added to the mainstream hydrogen is made into a molar ratio so that the amount of hydrogen / olefin is 1.1 or more and the number of divisions of the catalyst tank is increased, the mole ratio of hydrogen / olefin in each catalyst tank can be made higher. The total mixing molar ratio can be as close to 1.0 as possible. For example, the molar amount of hydrogen and the molar amount of olefins introduced into the lowermost catalyst tank are adjusted so that the hydrogen / olefin (molar ratio) is 1.1 or more, and introduced into the catalyst tank located upstream than the lowermost catalyst tank. The molar amount of hydrogen to be used and the molar amount of olefin are adjusted such that the hydrogen / olefin (molar ratio) is n + 1.1 or more (n is an integer indicating which stage upstream the catalyst tank in the upstream from the lowermost catalyst tank is). . When the mole ratio of hydrogen / olefin decreases, the reduction reaction of olefin becomes less likely to proceed. Therefore, it is preferable that the reduction reaction easily proceeds while the molar ratio of hydrogen / olefin becomes 1.1 or more at either point. The amount of hydrogen remaining in the paraffin produced after completion of the reduction reaction can be determined by how much the number of installations of the catalyst tank is increased.

In a preferred embodiment, the reduction reaction is performed at an internal temperature of 100 ° C or lower.

If the reaction temperature is too high or the amount of hydrogen to be added when the reduction reaction is performed, the olefin is decomposed to generate methane and ethane as impurities, so the reaction temperature is performed at 100 ° C. or lower, preferably 50 ° C. or lower. For this reason, for example, the catalyst tank is forcibly cooled from the outside using a cooling liquid or the like. If the temperature is too low, the olefin is liquefied and the reduction reaction is less likely to proceed. Therefore, when the operating pressure is 0.3 MPaG, it is necessary to set it to -76.3 ° C or more in ethylene and -12.0 ° C or more in propylene. The pressure at the time of the reduction reaction is usually 0.0 to 0.5 MPaG, and when the pressure is increased, the reduction reaction is in a direction in which the reaction is promoted, but the reaction temperature is increased by the heat of reaction. It is also not preferable to increase the pressure during the reduction reaction because the olefin is liquefied and becomes a liquid phase reaction.

In a preferred embodiment, the reduction catalyst charged in the catalyst tank is diluted with a dilution medium having no catalytic activity, and the mixing ratio of the dilution medium is gradually moved from the upstream side to the downstream side of the catalyst tank. It is supposed to be lowered.

According to this configuration, heat generated in the reduction reaction is transferred to the dilution medium, is easily dispersed and de-heated from the outside. On the other hand, since the mixing ratio of the dilution medium is to be lowered from the upstream side to the downstream side of the catalyst tank, the number of active sites of the catalyst is increasing toward the downstream side. For this reason, the olefin which flows through a catalyst tank is prevented from escaping unreacted, and the high purity paraffin is obtained.

When the reduction reaction is carried out, the larger the amount of the processing gas per unit cross-sectional area, the higher the amount of heat generated, and the decomposition reaction to methane or ethane, which is an impurity, is more likely to proceed, and the concentration of impurities is increased. For this reason, the smaller the gas flow velocity and the space velocity, the more preferable results are obtained. For example, the space velocity SV in the standard condition standard is 1000 / h or less, preferably 500 / h or less, including the dilution medium. On the other hand, if the space velocity is too large, the olefin does not sufficiently change the reaction into paraffins, leaving unreacted olefins.

In a preferred embodiment, the dilution medium includes a carrier supporting the catalytically active substance.

In a preferred embodiment, the catalytically active material consists of a metal containing at least one selected from palladium, rhodium, platinum, ruthenium and nickel.

In a preferred embodiment, the dilution medium contains an inorganic filler.

In a preferred embodiment, the olefin has 2 to 4 carbon atoms, and the paraffin has 2 to 4 carbon atoms.

The apparatus for producing paraffins provided by the second aspect of the present invention is an apparatus for producing paraffins by a reduction reaction proceeding in the presence of a reducing catalyst from olefins and hydrogen in a gaseous state, and a mainstream line for flowing hydrogen. And a plurality of catalyst tanks installed in series along the mainstream line, each having a gas introduction unit and a gas derivation unit, and containing the reduction catalyst, hydrogen supply means for supplying hydrogen to the mainstream line, It has a plurality of branching lines connected to the said mainstream line in the upstream of the said gas introduction part of a catalyst tank, It is characterized by including the olefin addition means for adding the said olefin via the said several branching line.

In a preferred embodiment, the number of installations of the catalyst tank is in the range of 2 to 5.

In a preferred embodiment, temperature adjusting means for adjusting the internal temperature of the catalyst tank is provided.

In a preferred embodiment, the reduction catalyst packed in the catalyst tank is diluted with a diluent medium having no catalytic activity, and comprises a plurality of catalyst regions having different mixing ratios of the dilution medium. The mixing ratio of the dilution medium in the plurality of catalyst zones is to be gradually decreased from the upstream side to the downstream side in the catalyst tank.

In a preferred embodiment, the number of batches of the catalyst zone is in the range of 2 to 5.

In a preferred embodiment, the dilution medium comprises a carrier carrying the catalytically active material.

In a preferred embodiment, the catalytically active material consists of a metal comprising at least one selected from palladium, rhodium, platinum, ruthenium and nickel.

In a preferred embodiment, the dilution medium comprises an inorganic filler.

In a preferred embodiment, hydrogen removal means is provided on the downstream side of the plurality of catalyst tanks in the mainstream line in order to remove hydrogen.

In a preferred embodiment, the hydrogen removing means includes a pressure swing adsorption gas separation device.

In a preferred embodiment, the hydrogen removing means includes a condenser.

According to the apparatus for producing paraffins having such a configuration, the method for producing paraffins according to the first aspect of the present invention can be appropriately performed.

Other features and advantages of the present invention will become more apparent from the following detailed description with reference to the accompanying drawings.

1 is a schematic configuration diagram showing an apparatus for producing paraffin according to a first embodiment of the present invention;
2 is a schematic block diagram showing an apparatus for producing paraffin according to a second embodiment of the present invention;
3 is a table showing a production example of propane when the number of installations of the catalyst tank is changed.

EMBODIMENT OF THE INVENTION Hereinafter, as a preferable embodiment of this invention, the method of manufacturing paraffin by reduction reaction from olefin and hydrogen is demonstrated concretely with reference to drawings.

[First Embodiment: When Two Catalyst Tanks]

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic block diagram which shows the manufacturing apparatus of paraffin which concerns on 1st Embodiment of this invention. The paraffin manufacturing apparatus X1 of this embodiment manufactures paraffin by the manufacturing method of paraffin which concerns on this invention from olefin and hydrogen in a gaseous state. The paraffin manufacturing apparatus X1 includes the hydrogen cylinder 1, the olefin cylinder 2, the liquor lines 21, 24, 26, a plurality of catalyst tanks 3, 4, The olefin line 22 and the branch lines 23 and 25 are provided. In addition, although the following description (it also includes the description of 2nd embodiment mentioned later) illustrates the case where olefin is propylene and the paraffin manufactured is propane, in this embodiment, olefin is ethylene or butene and paraffin is ethane. The same applies to the case of butane.

The hydrogen cylinder 1 is for supplying hydrogen to the liquor line 21, and is filled with high purity hydrogen gas under high pressure conditions.

The liquor lines 21, 24, and 26 are hydrogen supplied from the hydrogen cylinder 1, propylene added via branch lines 23 and 25 to be described later, and the catalyst tank 3 to be described later. In (4), it is a line for flowing the propane produced | generated by the reduction reaction, and is connected in series. In the liquor line 21, a pressure reducing valve 11, a flow meter 12, and a valve 13 are provided.

The catalyst tanks 3 and 4 are for producing paraffin (propane) by a reduction reaction which proceeds from olefin (propylene) and hydrogen in the presence of a reducing catalyst, and is used in mainstream lines (21), (24), ( It is installed in series along 26).

The catalyst tanks 3 and 4 have a closed tubular structure, and gas inlets 3a and 4a are provided at one end, and gas outlets 3b and 4b are provided at the other end. It is. The reduction catalyst is filled in the catalyst tanks 3 and 4. This reduction catalyst is for promoting the reduction reaction by hydrogen of olefin.

The reduction catalyst is configured to include a catalytically active substance having catalytic activity diluted with a dilution medium. The catalytically active substance consists of a metal containing at least one selected from palladium, rhodium, platinum, ruthenium and nickel, for example, palladium. In the present embodiment, the catalytically active substance is supported by a carrier to form a particle (catalyst particles), and the catalyst particles are diluted with an inorganic filler such as aluminum oxide balls, for example. The content rate of palladium (catalyst active material) in the said catalyst particle is 0.1 to 1.0 weight%, for example. Here, the carrier and the inorganic filler supporting the catalytically active substance also serve as a dilution medium.

The catalyst tank 3 includes a plurality of catalyst zones 301 and 302 (two in this embodiment). In this embodiment, the mixing ratio of the dilution medium (inorganic filler) in the catalyst regions 301 and 302 is different from each other, and is gradually stepped from the upstream side to the downstream side of the flow of gas in the catalyst tank 3. Can be reduced. For example, with respect to the catalyst region 301 located on the upstream side, the mixing ratio of the inorganic filler is 90 to 99 volume% (1 to 10 volume% of the catalyst particles), and the catalyst region 302 located on the downstream side. ), The mixing ratio of the inorganic filler is set to 80 to 90% by volume (10 to 20% by volume of catalyst particles).

The catalyst tank 4 includes a plurality of catalyst zones 401, 402, and 403 in the present embodiment. The mixing ratios of the inorganic fillers in the catalyst regions 401, 402, and 403 are different from each other, and can be decreased stepwise from the upstream side to the downstream side in the catalyst tank 4. For example, with respect to the catalyst region 401 located at the most upstream side, the mixing ratio of the inorganic filler is 90 to 99% by volume (1 to 10% by volume of catalyst particles), and the catalyst region 402 located in the middle. ), The mixing ratio of the inorganic filler is 80 to 90% by volume (10 to 20% by volume of the catalyst particles), and the catalyst region 403 located on the downstream side does not contain the inorganic filler ( That is, the mixing ratio of the inorganic filler is 0% by volume), and only the catalyst particles.

Jackets 32 and 42 are provided outside the catalyst tanks 3 and 4. The jackets 32 and 42 are for adjusting the internal temperature of the catalyst tanks 3 and 4, and are comprised so that the outer periphery of the catalyst tanks 3 and 4 may be enclosed. Cooling liquid as a temperature adjusting medium (cooling medium) is supplied to the jackets 32 and 42 via the lines 33 and 43.

The olefin cylinder 2 is for supplying the raw material olefin gas to the olefin line 22, and the raw material olefin gas is sealed under high pressure conditions. The olefin line 22 is provided with a pressure reducing valve 14.

The branch lines 23 and 25 are for adding the raw material olefin gas to the liquor lines 21 and 24, and each end portion communicates with the olefin line 22. As shown in FIG. The other end of the branch line 23 is connected to the liquor line 21, and the other end of the branch line 25 is connected to the liquor line 24. The branch line 23 is provided with a flow meter 15 and a valve 16. The branch line 25 is provided with a flow meter 17 and a valve 18.

The mainstream line 26 is provided with a pressure swing adsorption type gas separation device (PSA gas separation device) Y1 on the downstream side of the catalyst tanks 3 and 4. The PSA gas separation device Y1 is a line 61a connected to the adsorption tanks 6A and 6B filled with the adsorbent 60 which preferentially adsorbs paraffin (propane), and the adsorption tanks 6A and 6B. ) And (61f) and switching valves 62a to 62f provided in these lines, and the pressure fluctuation adsorption type gas separation method by appropriately switching the gas flow using the switching valves 62a to 62f. The gas separation operation by (PSA method) is performed. As the adsorbent 60 filled in the adsorption tanks 6A and 6B, for example, zeolite or activated carbon can be employed.

In the gas separation in the PSA gas separation device Y1, one cycle including, for example, an adsorption step and a desorption step is repeated in each of the adsorption tanks 6A and 6B. The adsorption step introduces a gas via the catalyst tank 4 into the adsorption tanks 6A and 6B via lines 61a and 6lb to adsorb propane in the gas to the adsorbent 60, and the adsorption is performed. It is a process for deriving the non-adsorbed gas which concentrated hydrogen from a tank. A desorption process is a process for depressurizing the inside of an adsorption tank, and desorbing propane from the adsorbent 60, and drawing out the desorption gas which propane concentrated.

A line 30 for flowing non-adsorbed gas is connected to the lines 61e and 61f. The line 30 is provided with a compressor 8, a cooler 9 and a buffer tank 10. In addition, a valve 31 is provided in the line 30, and an end of the line 30 is connected to the olefin line 22. Lines 29c and 61d are connected with a line 29 for flowing a desorption gas, and a product tank 7 is provided at an end of the line 29.

[Production Example of Propane in First Embodiment]

Next, the specific example of the method of manufacturing paraffin (propane) from an olefin (propylene) and hydrogen using the paraffin manufacturing apparatus (X1) of the said structure is demonstrated.

First, the hydrogen gas (Sumitomo Seika Co., Ltd. grade, EG grade) in the hydrogen cylinder 1 is, for example, a mainstream line at a flow rate of 104.3 Ndm ³ / h (N is a sign indicating a standard state) as a standard state quantity. 21 is supplied. Hydrogen gas in the liquor line 21 passes through the valve 13 while being regulated under reduced pressure from the pressure reducing valve 11 to 0.3 MPaG (G is a sign indicating a gauge pressure) and monitored by a flowmeter 12. It introduces into the catalyst tank 3 via the inlet port 3a.

On the other hand, propylene gas (made by Mitsui Chemical Co., Ltd.) as a raw material olefin gas is supplied from the olefin cylinder 2 to the olefin line 22. This propylene gas is 99.5 mol% of propylene and contains 0.5 mol% of propane as an impurity, and it is supplied with the flow volume of 99.4 Ndm <^3> / h in standard state. Olefin line 22 propylene gas, pressure 49.7 Ndm ³ / h the branch line 23 corresponding to the valve 14 after the pressure in 0.3㎫G adjusted up, the total flow rate 99.4Ndm ³ / h of the one-half of Enters, passes through valve 16 while being monitored by flow meter 15, and is added to liquor line 21. The propylene gas joined in the liquor line 21 is introduced into the catalyst tank 3 via the gas inlet 3a.

The catalyst tank 3 has an internal diameter of 30.7 mm and an overall filling height of the catalyst regions 301 and 302 is 800 mm. In the catalyst region 301, catalyst particles having a particle diameter of 3 mm (product of Nikki Shokubai Kasei Co., Ltd.), in which 0.5% by weight of palladium was supported on aluminum oxide (Al ₂ O ₃ ) serving as a carrier. , N1182AZ) 0.003dm ³ and aluminum oxide balls (HD-2) 0.293dm ³ (99.0% by volume) having a particle diameter of 3 mm are mixed, and a total of 0.296dm ³ is filled. The filling height is 400 mm. In the catalyst region 302, 0.030 dm ^{3 of} catalyst particles and 0.266 dm ³ (89.9 volume%) of aluminum oxide balls, which are the same as the catalyst region 301, are mixed, and a total of 0.296 dm ³ is filled. 400 mm.

With respect to the gas G1 (hydrogen gas and propylene gas) introduced into the catalyst tank 3, the mixing ratio (molar ratio) of hydrogen and propylene has hydrogen gas / propylene gas of 104.3 / 49.7 = 2.1, and hydrogen to propylene. Is in excess. The introduction gas G1 into the catalyst tank 3 passes through the catalyst regions 301 and 302 and is led to the gas outlet 3b. Here, the space velocity (SV) of hydrogen gas and propylene gas passing through the catalyst regions 301 and 302 is (104.3 + 49.7) / (0.296 × 2) = 260 / on a standard state basis. h becomes.

In the catalyst regions 301 and 302, the reduction reaction which is an exothermic reaction advances by the action of a reduction catalyst. That is, propane is produced | generated by the reduction reaction (hydrogenation reaction) by the hydrogen of propylene. In this reduction reaction, as can be seen from the chemical formula described in paragraph [0011], the number of moles of propylene consumed, the number of moles of hydrogen consumed and the number of moles of propane produced are equal. Here, the cooling liquid of 10 degreeC is supplied to the jacket 32 through the line 33, and the catalyst tank 3 is cooled from the outside, and the reaction temperature in the catalyst area 301, 302 is It adjusts so that it may become predetermined temperature (about 20 degreeC) of 100 degrees C or less.

In the reduction reaction of propylene (olefin) with hydrogen in the catalyst zones 301 and 302, since the catalytically active substance is diluted by the dilution medium, the local excessive temperature rise due to the exotherm accompanying the reduction reaction is Is prevented. In addition, through the flow of the cooling medium to the jacket 32, the internal temperature of the catalyst tank 3 can be adjusted more accurately. This contributes to the prevention of generation of impurities by decomposition of olefins occurring at high temperature and to promoting a reduction reaction. In the catalyst regions 301 and 302, all of the propylene in the inlet gas G1 becomes propane by a reduction reaction.

As a result of the reduction reactions in the catalyst regions 301 and 302, the gas G2 derived from the gas outlet 3b has a hydrogen gas content of 54.6 Ndm ^{3 /} h (104.3-49.7 = 54.6) and a propane gas amount. This 49.7 Ndm ³ / h adds up to 104.3 Ndm ³ / h. The gas G2 flows toward the next catalyst tank 4 through the mainstream line 24 and is introduced into the catalyst tank 4 via the gas inlet 4a.

On the other hand, 49.7 Ndm ³ / h corresponding to one-half of the propylene gas (total flow rate 99.4 Ndm ³ / h) in the olefin line 22 enters the branch line 25 and is monitored by the flow meter 17 while the valve ( Passed through 18, it is added to the liquor line 24. The propylene gas joined in the liquor line 24 is introduced into the catalyst tank 4 via the gas inlet 4a.

Similarly to the catalyst tank 3, the catalyst tank 4 has an internal diameter of 30.7 mm, while the total filling height of the catalyst zones 401, 402, and 403 is 900 mm. In the catalyst region 401, 0.5 wt% of palladium had a catalyst particle having a particle diameter of 3 mm (the same as the catalyst region 301 of the catalyst bath ³ ) 0.003dm ³ and a particle diameter 3 supported on aluminum oxide as a carrier. 0.2 mm dm ³ (99.0% by volume) of aluminum oxide balls (same as the catalyst zone 301 of the catalyst bath ³ ) were mixed, and a total of 0.296 dm ³ was filled, and the filling height thereof was 400 mm. In the catalyst region 402, 0.030 dm ^{3 of} catalyst particles similar to the catalyst region 401 and 0.266 dm ³ (89.9 volume%) of aluminum oxide balls having a particle diameter of 3 mm are mixed, and a total of 0.296 dm ³ is filled. Its filling height is 400 mm. In the catalyst region 403, only the catalyst particles similar to the catalyst region 401 are filled with 0.074 dm ³ , and the filling height thereof is 100 mm.

As for the gas G3 introduced into the catalyst tank 4, the mixing ratio (molar ratio) of hydrogen and propylene is 54.6 / 49.7 = 1.1 for hydrogen gas / propylene gas, and excess hydrogen for propylene. The introduction gas G3 to the catalyst tank 4 is led to the gas outlet 4b through the catalyst regions 401, 402, and 403. Here, the space velocity SV of the hydrogen gas and the propylene gas passing through the catalyst regions 401, 402, and 403 is (54.6 + 49.7) / (0.296 x 2 + 0.074) = 157 / h.

In the catalyst regions 401, 402, and 403, the reduction reaction, which is an exothermic reaction, proceeds by the action of the reduction catalyst. That is, propane is produced | generated by the reduction reaction of propylene with hydrogen. Here, the cooling liquid of 10 degreeC is supplied to the jacket 42 through the line 43, The catalyst tank 4 is cooled from the outside, In the catalyst area 401, 402, 403, The reaction temperature is adjusted to be a predetermined temperature (about 20 ° C). In the catalyst regions 401, 402, and 403, all of the propylene in the inlet gas G3 becomes propane by a reduction reaction.

As a result of the reduction reaction in the catalyst regions 401, 402, and 403, the gas G4 derived from the gas outlet 4b has a hydrogen gas content of 4.9 Ndm ³ / h (54.6-49.7 = 4.9). ), The amount of propane gas is 99.4 Ndm ³ / h (49.7 + 49.7 = 99.4), which is 104.3 Ndm ³ / h in total. The gas G4 flows toward the PSA gas separation device Y1 through the mainstream line 26.

The residual propylene concentration in the gas G4 (hereinafter, referred to as "manufacturing gas" appropriately) flowing through the liquor line 26 was analyzed by gas chromatography, which was less than 1 ppm and was below the detection limit. In the reduction reaction in the two tanks of the catalyst tanks 3 and 4, the total mixing molar ratio of hydrogen / propylene is 104.3 / 99.4 = 1.05, and hydrogen remains 4.7 mol% in the production gas.

Then, the production gas in the liquor line 26 is sent to the PSA gas separation device Y1, and by performing the gas separation operation described above, hydrogen as the non-adsorption gas is derived from the adsorption tanks 6A and 6B. Flows into the line 30. Hydrogen introduced into the line 30 is compressed in the compressor 8 and then cooled by the cooler 9 and recovered in the buffer tank 10. The recovered hydrogen passes through the valve 31 from the buffer tank 10, flows into the olefin line 22, and is recycled to the raw material system. On the other hand, in the gas separation operation in the PSA gas separation device Y1, the propane from which hydrogen has been removed is derived from the adsorption tanks 6A and 6B as desorption gas and passes through the line 29. It accumulates in the tank 7 as high purity propane (product gas).

In the production of paraffin (propane) of the present embodiment, by reducing reaction from olefin and hydrogen in a gaseous state, the reaction amount per unit volume of olefin (propylene) can be reduced, and the calorific value according to the reduction reaction can be reduced. have. When the reaction temperature is too high when the reduction reaction of olefin (propylene) is carried out, olefin is decomposed to generate impurities such as methane and ethane. In the present embodiment, however, by using the olefin gas as the raw material, even if a high concentration of the raw olefin gas is reacted, an extreme temperature rise is avoided, and the raw olefin gas can be substantially completely paraffinized.

In the above production example, a plurality of catalyst tanks 3 and 4 are separated and installed in series, and olefins (propylene) are separately added to each of the catalyst tanks 3 and 4 with hydrogen as the mainstream. have. Reduction reaction of olefin (propylene) with hydrogen is more likely to proceed by adding more hydrogen than the theoretical equivalent. Therefore, by dividing two sets of catalyst tanks 3 and 4 in series and dividingly adding olefin (propylene) with hydrogen as the mainstream, the amount of hydrogen in each of the catalyst tanks 3 and 4 / Olefin amount (molar ratio) can be made larger, and reduction reaction can be accelerated | stimulated. Moreover, since olefin (propylene) is divided and added, the raise of reaction temperature of each catalyst tank 3 and (4) vicinity can be suppressed.

The catalyst tanks 3 and 4 are adjusted so that the internal temperature may be a predetermined temperature of 100 ° C. or less by the cooling liquid flowing through the jackets 32 and 42 provided outside. Thereby, the heat generated by the reduction reaction in the catalyst tanks 3 and 4 can be efficiently sent out, and the reduction reaction can be performed at an appropriate reaction temperature.

Catalytically active substances (catalyst particles) are diluted in the reduction catalysts (catalyst regions 301, 302 and catalyst regions 401, 402, 403) packed in the catalyst tanks 3, 4. It contains what was diluted with the medium (inorganic filler), and the mixing ratio of an inorganic filler falls in steps from the upstream side of the catalyst tanks 3 and 4 to a downstream side. According to this configuration, heat generated in the reduction reaction is transferred to the inorganic filler, and is easily dispersed and de-heated from the outside. On the other hand, since the mixing ratio of the inorganic filler decreases from the upstream side to the downstream side of the catalyst tank, the number of active sites of the catalytically active substance is increasing toward the downstream side. For this reason, the olefin which flows through the catalyst tanks 3 and 4 is prevented from being released unreacted, and paraffin with high purity is obtained.

[Production Example of Ethane in First Embodiment]

Next, when olefin is ethylene, the method of manufacturing ethane from ethylene and hydrogen using the paraffin manufacturing apparatus X1 shown in FIG. 1 is demonstrated, for example.

From the olefin cylinder 2, a crude ethylene gas (manufactured by Nippon Fine Gas Co., Ltd.) having 99.4 mol% of ethylene and 0.6 mol% of ethane as impurities was flown at 99.4 Ndm ³ / h in a standard state. It supplied to the olefin line 22 by this, and it flowed into the catalyst tanks 3 and 4 at 49.7 Ndm <^3> / h in 2 parts. The size of the first tank 3 is 30.7 mm in internal diameter, and catalyst particles having a particle diameter of 3 mm in which 0.5% by weight of rhodium is supported on aluminum oxide (Al ₂ O ₃ ) in the upstream catalyst region 301. 0.293 dm ^{3 was} mixed and filled with 0.003 L (manufactured by Aldrich) and an aluminum oxide ball having a particle diameter of 3 mm, and the filling height was 400 mm. In the downstream catalyst region 302, 0.03 dm ^{3 of} catalyst particles and 0.266 dm ³ of aluminum oxide balls, which were the same as the catalyst region 301, were mixed, and a total of 0.296 dm ³ was filled, and the filling height thereof was 400 mm. The second tank 3 has an inner diameter of 30.7 mm and a catalyst particle having a particle diameter of 3 mm in which 0.5% by weight of rhodium is supported on aluminum oxide (Al ₂ O ₃ ) in the most upstream catalyst region 401. 0.003 and dm ^3, the 3㎜ of aluminum oxide ball 0.293dm ³ is filled with mixed, the middle catalyst zone (402) has an aluminum oxide ball, such as the catalyst zone 401. catalyst particles 0.030dm ³ and a catalyst zone 401, such as 0.266dm ³ was mixed and filled. The most downstream catalyst zone 403 was filled with only 0.074 dm ^{3 of} catalyst particles, such as catalyst zone 401. The filling heights of the catalyst regions 401, 402, and 403 are 400 mm in the catalyst region 401, 400 mm in the catalyst region 402, and 100 mm in the catalyst region 403. It was. Ethylene was added to each of the catalyst tanks 3 and 4 while flowing 104.3 Ndm ³ / h of hydrogen as the main stream in series with these two tanks 3 and 4 in series. In the catalyst tanks 3 and 4 (catalyst regions 301, 302, 401, 402, and 403), a reduction reaction with hydrogen of ethylene proceeds and the jacket 32 is externally present. Cooling control was carried out so that the inside of the catalyst tanks 3 and 4 might be set to about 20 degreeC, flowing a 10 degreeC cooling liquid into (42) and (42). As a result, when the residual ethylene concentration in the production gas drawn out from the gas outlet 4b of the second tank 3 was analyzed by gas chromatography (FID), it became less than 1 ppm which is less than the detection limit. Substantially all were reduced to ethane.

Second Embodiment: When Two Catalyst Tanks

2 is a schematic configuration diagram showing an apparatus for producing paraffin according to a second embodiment of the present invention. Paraffin manufacturing apparatus X2 of this embodiment is the same as paraffin manufacturing apparatus X1 shown in FIG. 1 about a basic structure, but the number of catalyst tanks is three tanks, and the fractionation for removing hydrogen in the downstream of a catalyst tank is carried out. It differs from the paraffin manufacturing apparatus X1 of the said 1st Embodiment in that the apparatus is provided. 2, the same code | symbol as the said embodiment is attached | subjected to the element similar or similar to 1st Embodiment, and description is abbreviate | omitted suitably.

The paraffin manufacturing apparatus X2 of 2nd Embodiment includes the hydrogen cylinder 1, the olefin cylinder 2, the liquor lines 21, 24, 26, 28, and several catalyst tanks. (3), (4), (5), the olefin line 22, the branch line 23, (25), and (27) are provided. Moreover, also in this embodiment, the case where an olefin is propylene and the paraffin manufactured is propane is illustrated and demonstrated.

In 2nd Embodiment, the catalyst tank 5 is added compared with 1st Embodiment, and according to the addition of this catalyst tank 5, the branch line 27, the flowmeter 19, the valve 20, and mainstream Line 28 is added.

In the second embodiment, the catalyst tank 4 includes two catalyst zones 401 and 402 similarly to the catalyst tank 3. The mixing ratio of the inorganic filler is 90 to 99% by volume for the catalyst region 401 located on the upstream side, and the mixing ratio of the inorganic filler is 80 to 90% relative to the catalyst region 402 located on the downstream side. It is volume%.

On the other hand, the catalyst tank 5 is comprised similarly to the catalyst tank 4 in 1st Embodiment, and contains three catalyst areas 501, 502, and 503, and a cooling liquid is externally A jacket 52 for flowing the gas is provided. For the catalyst region 501 located at the most upstream side, the mixing ratio of the inorganic filler is 90 to 99% by volume, and for the catalyst region 502 at the middle, the mixing ratio of the inorganic filler is 80 to 90%. The catalyst region 503 which is the volume% and is located on the most downstream side does not contain the inorganic filler (that is, the mixing ratio of the inorganic filler is 0 volume%), and consists only of the catalyst particles.

The liquor line 28 is provided with a condenser Y2 at the downstream side of the catalyst tanks 3, 4, and 5. The condenser Y2 includes a condenser 601 through a gas from the liquor line 28, a line 602 for flowing a cooling liquid for cooling outside the condenser 601, and a condenser 601. And a U-shaped tube 603 for flowing the liquefied propane. A line 30 for recovering residual gas is connected to the capacitor 601. The line 30 is provided with a compressor 8, a cooler 9 and a buffer tank 10. In addition, a valve 31 is provided in the line 30, and an end of the line 30 is connected to the olefin line 22. The valve 604 is provided in the U-shaped pipe 603, and the end of the U-shaped pipe 603 is opened in the product tank 7. The upper end of the product tank 7 is provided with a line 605 for returning the vaporized propane gas to the liquor line 28, and a valve 606 is provided at the line 605. A line 607 is connected to the line 602 in a branched shape, and a valve 608 is provided in the line 607. Outside the product tank 7, the jacket 72 is provided so that the outer periphery of the said product tank 7 may be enclosed. An end of the line 607 is connected to the jacket 72, and the cooling liquid for cooling is supplied to the jacket 72 via the line 607.

[Production Example of Propane in Second Embodiment]

Next, the specific example of the method of manufacturing paraffin (propane) from an olefin (propylene) and hydrogen using the paraffin manufacturing apparatus (X2) of the said structure is demonstrated.

First, hydrogen gas (same as the first embodiment) in the hydrogen cylinder 1 is supplied to the liquor line 21 at a flow rate of 104.3 Ndm ³ / h as a standard state amount, for example. The hydrogen gas in the liquor line 21 passes through the valve 13 while being regulated to 0.3 MPa by the pressure reducing valve 11 and monitored by the flowmeter 12, and passes through the gas inlet 3a to the catalyst tank. It is introduced in (3).

On the other hand, propylene gas (made by Mitsui Chemical Co., Ltd.) as a raw material olefin gas is supplied from the olefin cylinder 2 to the olefin line 22. This propylene gas is 99.99 mol% of propylene, and contains 0.01 mol% of propane as an impurity, and it is supplied by the flow volume of 100.3 Ndm <^3> / h in standard state. Olefin line 22 propylene gas, 33.4 Ndm ³ / h the branch line (23) corresponding to the back pressure in the pressure-adjusting valve 14 to 0.3㎫G, 1/3 of the total flow rate of 100.3 Ndm ³ / h of Enters, passes through valve 16 while being monitored by flow meter 15, and is added to liquor line 21. The propylene gas joined in the liquor line 21 is introduced into the catalyst tank 3 via the gas inlet 3a.

The catalyst tank 3 has an internal diameter of 30.7 mm and a total filling height of the catalyst regions 301 and 302 is 800 mm. In the catalyst region 301, a catalyst particle having a particle diameter of 3 mm (as in the first embodiment) 0.003dm ³ and an aluminum oxide ball having a particle diameter of 3 mm (0.5% by weight of palladium supported on an aluminum oxide serving as a carrier) As in the first embodiment), 0.293 dm ³ is mixed, and a total of 0.296 dm ³ is filled, and the filling height thereof is 400 mm. Further, in the catalyst zone 302, the catalyst zone 301 and the catalyst particles ³ and a particle size 0.030dm 3㎜ aluminum oxide balls of ³ 0.266dm a mixture of, a total 0.296dm ³ and is filled, the filling height 400 mm.

As for the gas G1 (hydrogen gas and propylene gas) introduced into the catalyst tank 3, the mixing ratio (molar ratio) of hydrogen and propylene has hydrogen gas / propylene gas of 104.3 / 33.4 = 3.1, and hydrogen to propylene. Is in excess. The introduction gas G1 to the catalyst tank 3 is led to the gas outlet 3b through the catalyst regions 301 and 302. Here, the space velocity SV of the hydrogen gas and the propylene gas passing through the catalyst regions 301 and 302 is (104.3 + 33.4) / (0.296 × 2) = 233 / h on a standard state basis.

In the catalyst regions 301 and 302, a reduction reaction which is an exothermic reaction proceeds by the action of a reduction catalyst. That is, propane is produced | generated by the reduction reaction of propylene with hydrogen. Here, the molar ratio of the hydrogen gas / propylene gas of the gas which flows into the catalyst tank 3 is set to 3.1, and it is hydrogen rather than the molar ratio 2.1 of the hydrogen gas / propylene gas of the gas which flows into the catalyst tank 3 shown in FIG. Since it is excess, compared with the case of the catalyst tank 3 of FIG. 1, a reduction reaction becomes easy to advance. 10 degreeC cooling liquid is supplied to the jacket 32 through the line 33, and the catalyst tank 3 is cooled from the outside, and reaction temperature in the catalyst area | regions 301 and 302 is 100 degrees C or less. It is adjusted so as to become a predetermined temperature (about 20 ° C). In the catalyst regions 301 and 302, all of the propylene in the inlet gas G1 becomes propane by a reduction reaction.

As a result of the reduction reactions in the catalyst regions 301 and 302, the gas G2 derived from the gas outlet 3b has a hydrogen gas amount of 70.9 Ndm ³ / h and a propane gas amount of 33.4 Ndm ³ / h. The total is 104.3 Ndm ³ / h. The gas G2 flows toward the next catalyst tank 4 through the mainstream line 24 and is introduced into the catalyst tank 4 through the gas inlet 4a.

On the other hand, 33.4 NL / h corresponding to one third of the propylene gas (total flow rate 100.3 Ndm ³ / h) in the olefin line 22 enters the branch line 25 and is monitored by the flow meter 17 while the valve 18 Is added to the liquor line 24. The propylene gas joined in the liquor line 24 is introduced into the catalyst tank 4 via the gas inlet 4a.

Similarly to the catalyst tank 3, the catalyst tank 4 has an internal diameter of 30.7 mm and the total filling height of the catalyst regions 401 and 402 is 800 mm. In the catalyst region 401, 0.5 wt% of palladium had a catalyst particle having a particle diameter of 3 mm (the same as the catalyst region 301 of the catalyst bath ³ ) 0.003dm ³ and a particle diameter 3 supported on aluminum oxide as a carrier. 0.293 dm ³ of aluminum oxide balls (same as the catalyst region 301 of the catalyst bath ³ ) are mixed, and a total of 0.296 dm ³ is filled, and the filling height thereof is 400 mm. In the catalyst zone 402, the catalyst zone 401 and the catalyst particle, such as particle size of ³ 0.030dm 3㎜ aluminum oxide balls of ³ 0.263dm are mixed, and the total 0.296dm ³ is filled, the filling height 400㎜ to be.

As for the gas G3 introduced into the catalyst tank 4, the mixing ratio (molar ratio) of hydrogen and propylene is 70.9 / 33.4 = 2.1 of hydrogen gas / propylene gas, and hydrogen is excessive with respect to propylene. The introduction gas G3 to the catalyst tank 4 is led to the gas outlet 4b through the catalyst regions 401 and 402. Here, the space velocity SV of the hydrogen gas and the propylene gas passing through the catalyst regions 401 and 402 is (70.9 + 33.4) / (0.296 × 2) = 176 / h on a standard state basis.

In the catalyst regions 401 and 402, a reduction reaction that is an exothermic reaction proceeds by the action of a reduction catalyst. That is, propane is produced | generated by the reduction reaction of propylene with hydrogen. Here, the cooling liquid of 10 degreeC is supplied to the jacket 42 through the line 43, and the catalyst tank 4 is cooled from the outside, and reaction temperature in the catalyst area 401, 402 is It is adjusted to be a predetermined temperature (about 20 ° C). In the catalyst regions 401 and 402, all of the propylene in the inlet gas G3 becomes propane by a reduction reaction.

As a result of the reduction reactions in the catalyst regions 401 and 402, the gas G4 derived from the gas outlet 4b has a hydrogen gas content of 37.4 Ndm ³ / h and a propane gas amount of 66.9 Ndm ³ / h. The total is 104.3 Ndm ³ / h. The gas G4 flows toward the next catalyst tank 5 through the mainstream line 26 and is introduced into the catalyst tank 5 via the gas inlet 5a.

On the other hand, 33.4 Ndm ³ / h corresponding to one third of the propylene gas (total flow rate 100.3 Ndm ³ / h) in the olefin line 22 enters the branch line 27 and is monitored by the flow meter 19 while the valve ( Passed through 20, it is added to the liquor line 26. The propylene gas joined in the liquor line 26 is introduced into the catalyst tank 5 via the gas inlet 5a.

Similarly to the catalyst tanks 3 and 4, the catalyst tank 5 has an internal diameter of 30.7 mm, while the total filling height of the catalyst regions 501, 502, and 503 is 900 mm. In the catalyst region 501, catalyst particles having a particle diameter of 3 mm (the same as the catalyst region 301 of the catalyst tank ³ ) 0.003dm ³ and a particle diameter 3, in which 0.5% by weight of palladium was supported on aluminum oxide as a carrier. 0.293 dm ³ of aluminum oxide balls (same as the catalyst region 301 of the catalyst bath ³ ) are mixed, and a total of 0.296 dm ³ is filled, and the filling height thereof is 400 mm. In the catalyst zone 502, the catalyst zone 501 and the catalyst particle, such as particle size of ³ 0.030dm 3㎜ aluminum oxide balls of ³ 0.263dm are mixed, and the total 0.296dm ³ is filled, the filling height 400㎜ to be. In the catalyst region 503, only 0.074 dm ³ of the same catalyst particles as the catalyst region 501 are filled, and the filling height thereof is 100 mm.

As for the gas G5 introduced into the catalyst tank 5, the mixing ratio (molar ratio) of hydrogen and propylene is 37.4 / 33.4 = 1.1 for hydrogen gas / propylene gas, and hydrogen is excessive with respect to propylene. The introduction gas G5 to the catalyst tank 5 is led to the gas outlet 5b through the catalyst regions 501, 502, and 503. Here, the space velocity SV of the hydrogen gas and the propylene gas passing through the catalyst regions 501, 502, and 503 is (37.4 + 33.4) / (0.296 x 2 + 0.074) = 106 / h.

In the catalyst regions 501, 502, and 503, a reduction reaction that is an exothermic reaction proceeds by the action of a reduction catalyst. That is, propane is produced | generated by the reduction reaction of propylene with hydrogen. Here, the cooling liquid of 10 degreeC is supplied to the jacket 52 through the line 53, and the catalyst tank 5 is cooled from the outside, In the catalyst area 501, 502, 503, The reaction temperature is adjusted to be a predetermined temperature (about 20 ° C). In the catalyst regions 501, 502, and 503, all of the propylene in the inlet gas G5 becomes propane by a reduction reaction.

As a result of the reduction reaction in the catalyst regions 501, 502, and 503, the gas G6 derived from the gas outlet 5b has a hydrogen gas amount of 4.0 Ndm ³ / h and a propane gas amount of 100.3 Ndm. ³ / h adds up to 104.3 Ndm ³ / h. The gas G6 is introduced into the capacitor 601 of the partial condenser Y2 through the mainstream line 28.

The residual propylene concentration in the gas G6 (manufacturing gas) flowing through the liquor line 28 was analyzed by gas chromatography, which was less than 1 ppm and was below the detection limit. In the reduction reaction in all three tanks of the catalyst tanks 3, 4, and 5, the total mixing mole ratio of hydrogen / propylene is 104.3 / 100.3 = 1.04, and hydrogen is 3.8 mol% in the production gas. Remains.

The production gas in the liquor line 28 is introduced into the capacitor 601 of the power storage device Y2. The capacitor 601 is supplied with a cooling liquid of -20 to -10 ° C from the outside through the line 602, and propane is cooled and condensed under about 0.3 MPaG. Uncondensed residual hydrogen is compressed in compressor 8 via line 30 and then cooled by cooler 9 and recovered in buffer tank 10. The recovered hydrogen passes through the valve 31 from the buffer tank 10, flows into the olefin line 22, and is recycled to the raw material system. On the other hand, hydrogen is removed and the liquefied propane accumulates as high purity propane in the product tank 7 via the U-shaped tube 603.

In the production example of the second embodiment, the plurality of catalyst tanks 3, 4, and 5 are separated and installed in series, and each of the catalyst tanks 3, 4, and (with hydrogen as the mainstream). The olefin (propylene) is divided and added to 5). The reduction reaction of hydrogen of the olefin (propylene) with hydrogen is more likely to proceed by adding more hydrogen than the theoretical equivalent. Therefore, each of the three catalyst tanks 3, 4, and 5 is divided in series, and hydrogen is used as the mainstream to divide and add olefins (propylene) in each of the catalyst tanks 3, 4, and 5. The amount of hydrogen / olefin amount (molar ratio) in) can be made larger, and a reduction reaction can be promoted. Moreover, since olefin (propylene) is divided and added, the raise of reaction temperature of each catalyst tank 3, (4), and (5) vicinity can be suppressed.

In addition, the ratio of the amount of hydrogen and the amount of olefins in the introduction gas (G1), (G3), or (G5) to the catalyst tanks (3), (4), (5) is the amount of hydrogen / olefin (molar ratio) It is 1.1 or more, and the amount of olefins in the introduction gas (G1), (G3), (G5) to each of the catalyst tanks 3, (4), (5) is equal. Since the mainstream hydrogen passes through the catalyst tanks 3, 4, and 5 sequentially and is consumed in the reduction reaction with the olefin, the hydrogen / olefin is 1.1 or more in the most downstream catalyst tank 5. The amount of olefins is set as possible. Thereby, in the introduction gas G3 to the catalyst tank 4 (one upstream side of the catalyst tank 5), the amount of hydrogen added in the reduction reaction in the catalyst tank 5 with respect to the amount of hydrogen And the amount of hydrogen / olefin is 2.1 or more. Similarly, in the introduction gas G1 to the catalyst tank 3 (one upstream side of the catalyst tank 4), the amount of hydrogen consumed by the reduction reactions in the catalyst tanks 4 and 5 with respect to the amount of hydrogen. It becomes the amount which added and the amount of hydrogen / olefin becomes 3.1 or more.

In the case of three tanks in series, the total mixing molar ratio of hydrogen / propylene becomes 1.04 as described above, and the amount of propane gas in the production gas (104.3 Ndm ³ / h) is 100.3 Ndm ³ / h, and the amount of hydrogen gas This is 4.0 Ndm ³ / h and the residual hydrogen concentration is 3.8 mol%. In the case of FIG. 1 in which two tanks are used in series (the amount of propane gas in the production gas is 99.4 NL / h, the amount of hydrogen gas is 4.9 Ndm ³ / h, and the residual hydrogen concentration is 4.7 mol%). Even when Ndm ³ / h) is used, the production amount of propane is increased by 1% and the residual hydrogen concentration is reduced by 0.9 mol%. Thus, an effect of adding one tank of catalyst is provided. In addition, since the amount of heat generated by the reaction heat of each catalyst tank is reduced by 30% or more, it is easy to perform external cooling and temperature control.

It is shown in the table | surface of FIG. 3 compared with the case where the production example of propane when only one pair is produced when a catalyst tank is divided in series and the number of installations is sequentially increased to 2-5 tanks.

In each of the catalyst tanks except the final catalyst tank, the catalyst particles having a particle size of 3 mm and aluminum oxide balls having a particle diameter of 3 mm with 0.5 wt% of palladium supported on aluminum oxide (Al ₂ O ₃ ) on the upstream side were 1:99. The catalyst regions mixed and filled at a capacity of and the catalyst regions mixed and filled at 10:90 were respectively laminated at a packing height of 400 mm. Then, only the catalyst particles were filled to the filling height of 100 mm only in the final catalyst tank (in the case of one tank, the catalyst tank became the final catalyst tank). Each catalyst tank was operated by controlling reaction temperature to 20 degreeC, cooling with a cooling liquid.

When the amount of mainstream hydrogen as source gas is 104.3 Ndm ³ / h and the catalyst tank is 2 tanks, when the molar ratio of hydrogen gas / propylene gas of the introduction gas to each catalyst tank is 1.1 or more, the amount of propylene gas as source gas is 99.4 Ndm. ³ / h, and the total mixed molar ratio of hydrogen / propylene was 1.05. As a result, when the unreacted residual propylene concentration, the methane concentration, or the ethane concentration, which is an impurity in the production gas, were measured by gas chromatography (FID), the detection limit was less than 1 ppm, respectively, and the propylene was substantially completely reduced to propane. However, the remaining excess hydrogen amounted to 4.9 Ndm ³ / h, leaving 4.7 mol% in the production gas.

Next, when the number of installations of the catalyst tank is increased to 3, 4, or 5 tanks while the molar ratio of hydrogen gas / propylene gas of the introduction gas to each catalyst tank is 1.1 or more, the total mixing mole ratio of hydrogen / propylene becomes small and remains. The amount of hydrogen decreased, the amount of produced propane gas increased, and the calorific value of each catalyst tank decreased. However, when the molar ratio of hydrogen gas / propylene gas in the introduction gas to the catalyst tank was lowered to 1.0, the amount of propane gas as the production gas increased, but the residual hydrogen amount became 0, and the reduction reaction did not proceed completely. When measured by gas chromatography (FID), 5 ppm of residual propylene concentration, 2 ppm of methane as an impurity, and 1 ppm of ethane were detected in manufacturing gas. From this result, in order to ensure 100% reduction in each catalyst tank, the molar ratio of hydrogen gas / propylene gas in the introduction gas of each catalyst tank needs to be 1.1 or more.

When only one tank is used, the amount of mainstream hydrogen as source gas flows 104.3 Ndm ³ / h, and the amount of propylene gas as source gas flows 94.8 Ndm ³ / h so that the molar ratio of hydrogen gas / propylene gas is 1.1 or more. Introduced to the catalyst tank. As a result, the unreacted residual propylene concentration in the production gas was below the detection limit, but the concentration of methane as an impurity was 4 ppm and the ethane concentration was 3 ppm. Propylene was completely reduced to propane, but the excess amount of hydrogen remaining was the highest at 9.5 Ndm ³ / h. Here, methane or ethane is detected as a cause of detection of two or more tanks, and the heat of reaction is dispersed per catalyst tank, and the increase in reaction temperature is suppressed. It is considered that the temperature suppression effect by the above is not obtained. In addition, if there is only one tank and the molar ratio of hydrogen / propylene of the source gas is 1.1, it becomes relatively smaller than the hydrogen / propylene ratio of the catalyst tank in the case where the catalyst tank is two or more tanks (for example, in the case of two tanks) The first set of hydrogen / propylene ratios is 2.1, and in the case of three sets of catalyst tanks, the first set of hydrogen / propylene ratios is 3.1 and the second set of hydrogen / propylene ratios is 2.1). For this reason, it is considered that decomposition of propylene tends to occur in one tank of a reaction tank, and methane and ethane are produced | generated.

[Possibility of deformation]

As mentioned above, although specific embodiment of this invention was described, the scope of the present invention is not limited to the said embodiment below. The specific configuration of the apparatus for producing paraffins according to the present invention and the method for producing paraffins according to the present invention can be variously changed without departing from the spirit of the invention.

In the above two embodiments, the catalytically active substance is diluted with a dilution medium, and the catalyst particles having the catalytically active substance (palladium or rhodium) supported by a carrier are diluted with an inorganic filler (aluminum oxide ball), Although the case where the mixing ratio of the said inorganic filler is made to differ step by step was demonstrated as an example, this invention is not limited to this. For example, as a dilution method of the catalytically active substance, the proportion of the catalytically active substance supported on the carrier may be increased in steps of 0.1% by weight, 0.2% by weight, 0.5% by weight and the like without using an inorganic filler. In addition, the same effect as the method of dilution using an inorganic filler is obtained. As the catalytically active substance, a metal containing at least one selected from platinum, ruthenium and nickel may be used instead of palladium or rhodium. The catalytically active substance is not limited to the aspect supported by the carrier (Al ₂ O ₃ ), and may be used alone. As an inorganic filler, it is not limited to ceramic materials, such as an aluminum oxide ball, You may use the metal ball which consists of iron, stainless steel, etc.

In addition, the olefin as source gas is not limited to propylene and ethylene mentioned above, For example, butene which is in a gaseous state at normal temperature (about 20 degreeC) may be used.

X1, X2: paraffin manufacturing unit Y1: PSA gas separation unit
Y2: Decliner 1: Hydrogen Cylinder
2: propylene cylinder 3, 4, 5: catalyst tank
6A, 6B: adsorption tank 7: product tank
8: compressor 9: cooler
10: buffer tank 11, 14: pressure reducing valve
12, 15, 17, 19: flow meter 13, 16, 18, 20, 31: valve
21, 24, 26, 28: liquor line 22: olefin line
23, 25, 27: branch line 29, 30: line
32, 42, 52, 72: jacket 33, 43, 53: line
60: adsorbent
61a, 6lb, 61c, 61d, 61e, 61f: line
62a, 62b, 62c, 62d, 62e, 62f: switching valve
301, 302, 401, 402, 403, 501, 502, 503: catalyst zone
601: condenser 602, 605, 607: line
603: U-shaped pipe 604, 606, 608: valve

Claims (20)

A process for producing paraffins by reduction reactions proceeding in the presence of a reducing catalyst from olefins and hydrogen in a gaseous state,
A plurality of catalyst tanks each filled with the reduction catalyst are provided in series along a mainstream line through which hydrogen flows.
Each of the catalyst tanks has a plurality of catalyst zones filled with dilution media having no catalytic activity of the same type of reduction catalyst for adding hydrogen to olefins and converting them into paraffins.
The mixing ratio of the dilution medium is to be lowered in stages from the upstream side catalyst zone to the downstream side catalyst zone,
The method for producing paraffin, characterized in that the olefin is dividedly added to the mainstream line such that the molar amount of hydrogen introduced into each of the catalyst tanks is greater than the molar amount of olefins introduced into each of the catalyst tanks in the gas state. The method for producing paraffin according to claim 1, wherein the molar amount of hydrogen and the molar amount of olefins introduced into the respective catalyst tanks are adjusted so that hydrogen / olefin (molar ratio) is 1.1 or more. The method for producing paraffin according to claim 1 or 2, wherein the molar amount of olefins introduced into each of the plurality of catalyst tanks is equal. delete The method of claim 1, wherein the dilution medium comprises a carrier that carries a catalytically active material. The method of claim 5, wherein the catalytically active material is made of a metal comprising at least one selected from palladium, rhodium, platinum, ruthenium, and nickel. The method of claim 1, wherein the dilution medium comprises an inorganic filler. The method for producing paraffin according to claim 1 or 2, wherein the olefin has 2 to 4 carbon atoms and the paraffin has 2 to 4 carbon atoms. The molar amount of hydrogen and the molar amount of olefin introduced into the catalyst tank located in the downstream are adjusted so that hydrogen / olefin (molar ratio) may be 1.1 or more, and it is upstream than the said downstream catalyst tank. The molar amount of hydrogen and the molar amount of olefins introduced into the catalyst tank located at is equal to or higher than the hydrogen / olefin (molar ratio) of at least n + 1.1 (n represents which stage upstream from the downstream catalyst tank is the upstream catalyst tank). Integer) to be a method for producing paraffins. An apparatus for producing paraffin using the method of claim 1,
A liquor line for flowing hydrogen;
A plurality of catalyst tanks installed in series along the mainstream line, each of which has a gas introduction unit and a gas derivation unit, and which is filled with the reduction catalyst;
Hydrogen supply means for supplying hydrogen to the liquor line; And
An olefin addition means for adding said olefin via said branch line, having a branch line connected to said mainstream line at an upstream side of said gas introduction section of each catalyst tank;
The catalyst tank has a plurality of catalyst zones filled with a dilution medium in which the same type of reduction catalyst that adds hydrogen to olefins and converts it into paraffins is diluted with a dilution medium having no catalytic activity,
The mixing ratio of the dilution medium in the plurality of catalyst zones is to be gradually decreased from the upstream catalyst zone in the catalyst tank toward the downstream catalyst zone. The apparatus for producing paraffin according to claim 10, wherein the number of installations of the catalyst tank is in the range of 2 to 5. The paraffin manufacturing apparatus according to claim 10 or 11, further comprising a temperature adjusting means for adjusting an internal temperature of the catalyst tank. delete The apparatus for producing paraffin according to claim 10 or 11, wherein the number of batches of the catalyst region in each of the catalyst tanks is in the range of 2 to 5. The apparatus for producing paraffin according to claim 10 or 11, wherein the dilution medium comprises a carrier supporting a catalytically active substance. The apparatus of claim 15, wherein the catalytically active material is made of a metal including at least one selected from palladium, rhodium, platinum, ruthenium and nickel. The apparatus of claim 10 or 11, wherein the dilution medium comprises an inorganic filler. The paraffin production apparatus according to claim 10 or 11, wherein hydrogen removal means is provided on the downstream side of the plurality of catalyst tanks in the mainstream line to remove hydrogen. 19. The apparatus for producing paraffin according to claim 18, wherein the hydrogen removing means comprises a pressure swing adsorption gas separation device. The apparatus for producing paraffin according to claim 18, wherein the hydrogen removing means comprises a condenser.

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