The catalyst for the conversion of aliphatic hydrocarbons, c2-c12the method of its production and the way of transformation of aliphatic hydrocarbon, c2-c12in high-octane gasoline and/or aromatic hydrocarbons

 

(57) Abstract:

The invention relates to the refining and petrochemical industries, in particular to methods of producing catalysts for the conversion of aliphatic hydrocarbons WITH2-C12in high-octane gasoline and/or aromatic hydrocarbons. The purpose of the invention is the obtaining of an active and selective catalyst for the conversion of aliphatic hydrocarbons2-C12in high-octane gasoline and/or aromatic hydrocarbons. The technical result is achieved by the fact that the proposed catalyst for the conversion of aliphatic hydrocarbons2-C12in high-octane gasoline and/or aromatic hydrocarbons contains 60,0-80,0 wt.% zhelezohromovye with the structure of high zeolite ZSM-5 c silicate module SiO2/Al2O3= 20-160, SiO2/Fe2O3= 30-5000 modifying additive selected at least from the group of oxides of copper, zinc, gallium, lanthanum, molybdenum, rhenium in an amount of 0.1-10.0 wt.%; hardening additive is an oxide of boron, phosphorus, or mixtures thereof in the amount of 0.5-5.0 wt.%; connecting aluminum oxide - the rest is up to 100.0 wt.%. The catalyst was prepared by dry mixing the original sadmasu, drying the catalyst formed during thermal treatment for 0.1 to 24 hours the catalyst composition provides an increase in activity and selectivity of the catalyst, allows to increase the output of high-octane gasoline and/or aromatic hydrocarbons from aliphatic hydrocarbons2-C12and the process of transformation of aliphatic hydrocarbons2-C12carried out in the presence of the above catalyst at flow rate of 0.5 to 5.0 h-1and a pressure of 0.1 to 1.5 MPa. 3 ad and 1 C.p. f-crystals, 1 table.

The invention relates to the refining and petrochemical industries, in particular to methods of producing catalysts for the conversion of aliphatic hydrocarbons, C2-C12in high-octane gasoline and aromatic hydrocarbons.

The main industrial process of producing high octane gasoline and aromatic hydrocarbons is catalytic reforming of straight-run gasoline fractions, which is held at high temperatures between 450 and 550 C, the high pressure of 0.1 to 3.5 MPa and a hydrogen-containing gas. Disadvantages of the process of catalytic reforming of straight-run gasolines are the use of expensive Pt-containing produce the polar hydrocarbons WITH2-C12in high-octane gasoline or aromatic hydrocarbons (U.S. Pat. EN N 2144845, 01 J 29/44, WITH 10 G 35/095, 1998; U.S. Pat. EN N 2144846, 01 J 29/44, WITH 10 G 35/095, 1998; U.S. Pat. EN N 2144847, 01 J 29/44, WITH 10 G 35/095, 1998). According to the methods of the transformation of low molecular weight hydrocarbons2-C12in high-octane gasoline or aromatic hydrocarbons is carried out on the catalysts containing zeolite family pentasil with silicate module SiO2/Al2O3=20-80, modified zinc oxide, platinum, boron oxide or phosphorus oxide, or boron oxide and phosphorus oxide, the binder is alumina.

Major General shortcomings of the described methods for producing catalysts are the use of expensive Pt-modifier and low yield of liquid products of reaction.

Known zeolite-containing catalyst for the conversion of aliphatic hydrocarbons WITH2-C12in a high-octane component of gasoline or a concentrate of aromatic hydrocarbons containing high-silica group zeolite with a molar ratio of SiO2/Al2O3=20-80 mol/mol and a residual content of sodium oxide is not more than 0.4 wt.%, zinc oxide, gallium mixture of two or more oxides redkozemelnaja (U.S. Pat. EN N 2172212, 29/46 01 J, 10 G 35/095, 1999). The composition of the catalyst increases the yield of liquid hydrocarbons FROM5+and the increase in the content of aromatic hydrocarbons.

The disadvantages of this method are the multi-stage cooking, the complex composition of multicomponent catalyst and not a high yield of high octane component of gasoline.

A method of obtaining high zeolites of type ZSM-5 (U.S. Pat. EN N 1527154, 01 33/28, 1987). High zeolites of type ZSM-5 with silicate module SiO2/Al2O3=30-200 get the hydrothermal crystallization of a reaction mixture at 120-180 C for 1-7 days, containing sources of silicon oxide, aluminum oxide, alkali metal oxide, hexamethylenediamine were, and water. The degree of crystallinity of the obtained product 85-100%, the catalytic stability in the conversion of methanol 460-1100 hours To improve the stability of high zeolites in the H form is subjected to mechanical grinding to a particle size of 0.1 to 1.0 μm and thermoprotei processing steam at 520 C for 50 h

The disadvantage of the catalyst is not a high yield of liquid products such as high octane gasoline from aliphatic uglev -C12in a high-octane component of gasoline or a concentrate of aromatic hydrocarbons adopted for the prototype (U.S. Pat. EN N 2165293, 01 J 29/40, WITH 10 G 35/095, 2000). The catalyst contains, wt%: the group zeolite with a molar ratio of SiO2/Al2ABOUT3=20-150 and the residual content of sodium oxide is not more than 0.4 wt.% 20,00-90,00; zinc oxide 0,10-6,00 and/or gallium oxide 0,10-3,00; mixture of two or more oxides of rare earth elements selected from the group CE, La, Nd, Pr 0,10-5,00; iron oxide (III) 0,01-2,00; magnesium oxide is 0.01 -2,00; calcium oxide 0,01-2,00; a binder component - the rest.

The disadvantages of this catalyst, taken as a prototype, is a multi-stage cooking, the complex composition of multicomponent catalyst and not a high yield of high octane component of gasoline.

A method of obtaining high-octane gasoline, where the hydrocarbon fraction with a high content of hydrocarbons2-C5with the temperature of the end of the boil in the temperature range of boiling gasoline, fractionary emitting fraction2-C5and/or stable gasoline (fraction C5+) or light gasoline (FR. WITH5- (60-80) and heavy gasoline (FR. >(60-80). Fraction WITH2-C5or its mixture with Gator is the products of pyrolysis of mixed or stable, or heavy gasoline together and subjected to contacting with a zeolite-containing catalyst, products, contact share with the release of hydrocarbon gases WITH1-C4and liquid high-octane gasoline fraction, from which the rectification allocate target high-octane gasoline (FR. N. K. -195 C) and the residual fraction > 185; or the products of pyrolysis of pre-fractionary with gaseous (sin) and liquid (pyrolysis condensate fraction) fractions, sin is mixed with these factions together and subjected to contacting with the catalyst, and the pyrolysis condensate fraction compounding with high-octane gasoline fraction to its rectification or gasoline, selected after its rectification. As the catalyst used zeolites with structure of ZSM-5-11, supported on a carrier, or without consent, including modified elements II, III, V, VI and VIII groups, prepared by known methods. Optimal contact conditions: reaction temperature 300-480 C, a pressure of 0.2 to 4 MPa, the feed rate 1-6 h-1.

The disadvantages of this method are the multistage and the complexity of the process of producing high octane gasoline.

A method of obtaining vysokooktanovuju boiling gasoline, subjected to serial communication in the reaction zone with a catalyst based on zeolite ZSM-5 or ZSM-11, including modified items I, II, III, IV, and VIII groups (U.S. Pat. EN N 2039790, WITH 10 G 35/095, 1993). At the same time in each subsequent zone is subjected to contacting a light gasoline fraction of the previous zone, and heavy gasoline fractions zones mixed with products of last contact zone.

The disadvantages of this method are the multistage and the complexity of the process of producing high octane gasoline fractions and aromatic hydrocarbons.

The known method of producing high octane gasoline fractions and aromatic hydrocarbons (U.S. Pat. EN N 2163624, WITH 10 G 35/095, 1998). According to this method the transformation of hydrocarbons and/or oxygen-containing compounds is carried out at a temperature 280-460 C, a pressure of 0.1-4.0 MPa and in the presence of hydrogen-containing gas with a catalyst containing a zeolite with structure of ZSM-5 or ZS-11, in the crystal lattice which consists of atoms of aluminum and iron, with subsequent separation of the products contacting gaseous and liquid fractions, the stage contacting is performed with a catalyst containing zeolite total empirically elements or compounds of elements of V, VI, VII and VIII groups in the amount of 0.05-5.0 wt.%.

The disadvantages of this method are the complexity of the preparation of the catalyst and not a high yield of high octane gasoline fractions and aromatic hydrocarbons from hydrocarbon raw materials.

The closest to the essence of the technical solution is a way of turning aliphatic hydrocarbon, C2-C12in a high-octane component of gasoline or a concentrate of aromatic hydrocarbons is carried out at a temperature of 250-650 C, a pressure of 0.1-4.0 MPa and space velocity of the raw material is 0.1 to 10.0 h-1in the presence of a catalyst containing a group zeolite with a molar ratio of SiO2/Al2ABOUT3=20-150 mol/mol and with a residual content of sodium oxide is not more than 0.4 wt.%, zinc oxide and/or gallium oxide, and in any ratio of two or three oxide from the group of rare earth elements selected from the group CE, La, Nd, Pr, binder additionally contains iron oxide (III), magnesium oxide and calcium oxide (U.S. Pat. EN N 2165293, 01 J 29/40, WITH 10 G 35/095, 2000).

The disadvantages of this method are the multistage get, the complex composition of multicomponent catalyst and not a high yield of aromatic hydrocarbons is RA process of converting aliphatic hydrocarbons2-C12in high-octane gasoline and/or aromatic hydrocarbons.

The technical result is achieved by the fact that the proposed catalyst for the conversion of aliphatic hydrocarbons2-C12in high-octane gasoline and/or aromatic hydrocarbons receive a dry mixture of N-forms zhelezohromovye with the structure of the high-type zeolite H-ZSM-5 with silicate module SiO2/Al2O3=20-160, SiO2/Fe2O3=30-5000 at least one compound from the group of copper, zinc, gallium, lanthanum, molybdenum, rhenium in an amount of 0.1-10.0 wt.%, as the modifying metal; with a compound of boron, phosphorus, or mixtures thereof in an amount of 0.1-5.0 wt.%, as a hardening additive; with boehmite or alumina - the rest is up to 100.0 wt.%, as a binder; followed by mechanochemical processing in a vibrating mill for 0.1 to 72 hours, by forming the catalyst mass into granules or pellets, and drying the catalyst formed during the heat treatment at 550-600 C for 0.1 to 24 hours

Increased activity of the catalyst and the yield of aromatic hydrocarbons from hydrocarbon feedstock is achieved by obtaining zhelezohromovye with the structure of vysokorentabelno - modifiers in an amount of 0.1-10.0 wt.% allows to increase the output of high-octane gasoline and aromatic hydrocarbons from aliphatic hydrocarbons2-C12.

Telesolutions (JAS) with the structure of the high-type zeolite H-ZSM-5 get the hydrothermal crystallization at 120-180 C for 0.5 to 7 days the reaction mixture containing a source of cations of alkali metal, silicon oxide, aluminum oxide, iron oxide, hexamethylenediamine were (R) and water in the ratio of SiO2/Al2O3=20-160; SiO2/Fe2O3=30-5000; H2O/SiO2=20-80; R/SiO2=0,03-1,0; HE-/ SiO2=0,076-0,6; Na+/ SiO2=0,2-1,0 (U.S. Pat. EN N 1527154, 01 33/28, 1987) or other known methods. After crystallization of the zeolite is washed with distilled water, dried at 110 With 2-12 h and calcined at 550-600 C for 4-12 h In IR-spectra obtained JAS observed absorption band at 445, 550, 810 cm-1and a broad band in the region of 1000-1300 cm-1characteristic of high zeolite ZSM, the degree of crystallinity obtained JAS is 85-100%. According to x-ray analysis and infrared spectroscopy obtained JAS identical to the zeolite ZSM-5.

For translation in the N-form telesolutions d dried at 110 and calcined at 550-600 6 o'clock

The catalyst for the conversion of aliphatic hydrocarbons, C2-C12in high-octane gasoline and/or aromatic hydrocarbons receive a dry mixture of N-forms JAS with silicate module SiO2/Al2O3=20-160, SiO2/Fe2O3=30-5000 structure type zeolite H-ZSM-5, at least one compound from the group of copper, zinc, gallium, lanthanum, molybdenum, rhenium or mixtures thereof in an amount of 0.1-10.0 wt.%, as the modifying metal; with a compound of boron, phosphorus, or mixtures thereof in an amount of 0.1-5.0 wt.% as a hardening additive; with boehmite or alumina - the rest is up to 100.0 wt.% as a binder. Then the mixture is subjected to mechanochemical treatment in a vibrating mill for 0.1 to 72 hours, then the catalyst mass is molded, dried and calcined at 550-600 C for 0.1 to 24 hours Under the action of mechanical and high-temperature treatments of the mixture JAS, components, compounds modifying metals, hardening and binding agents happen modification JAS active components, the formation and the formation of active and selective catalyst.

The synthesized zeolite catalysts (both before and after mixing with components) can store the invention is illustrated by the following examples.

Example 1. To 200 g of water glass (29% SiO2, 9% Na2O 62% H2O) was added with stirring to 11.8 g of diamine (R) in 100 ml of N2Oh, 24,15 g of Al(NO3)3N2About 160 ml of N2About 1 g of "seed" high zeolite and poured a 0.1 n solution NGO3. The resulting mixture was loaded into an autoclave of stainless steel, is heated to 175-180 C and maintained under stirring 2-6 days, and then cooled. The synthesized product is washed with water, dried and calcined at 550-600 C for 12 hours To transfer in the H-form zeolites decationized processing 25% solution of NH4Cl (10 ml per 1 g of zeolite) at 90 C for 2 h, then washed with water, dried at 110 and calcined at 540 C for 6 hours Get H-ZSM-5 with silicate module SiO2/Al2O3=30, the degree of crystallinity of the product is 96%.

Then 70 g of H-ZSM-5 with silicate module SiO2/Al2O3=30 mixed with 35,29 boehmite lO(HE) and subjected to mechanochemical treatment in a vibrating mill for 8 hours the resulting powder was formed into pellets or tablets, dried 2 h at 20 or 30, then at 110 C for 3-4 h and calcined in air for 8 h at 550-600 C.

The obtained zeolite catalyst has a composition, wt.%:

H-ZSM-5 (SiO2/AlB>O3=50 receives the same way as in example 1, but instead 24,15 g of Al(NO3)39 H2O take 14,475 g of Al(NO3)39 H2O.

The obtained zeolite catalyst has a composition, wt.%:

H-ZSM-5 (SiO2/Al2O3=50) 70

Al2ABOUT330

Example 3. Telesolutions with the structure of zeolite H-ZSM-5 receive the same as in example 1, but instead 24,15 g of Al(NO3)39 H2About take 12,07 g of Al(NO3)39 H2O and 12,08 g Fe(NO3)39 H2O. Get telesolutions structure type zeolite H-ZSM-5 with silicate module SiO2/Al2O3=60, SiO2/Fe2O3=65.

Then 70 g of JAS with silicate module SiO2/Al2O3=60, SiO2/Fe2O3=65 mix from 1.77 g of N3IN3with the volume of 34.12 g lO(HE) and subjected to mechanochemical treatment in a vibrating mill for 8 hours the resulting powder was formed into pellets or tablets, dried for 2-3 h at 20 or 30, then at 110 C for 3-4 h and calcined in air for 8 h at 550-600 C.

The obtained zeolite catalyst has a composition, wt.%:

Telesolutions 70

IN2ABOUT31

Al2ABOUT329

Example 4. Telesolutions with structure is 3)39 H2O and 1.45 g Fe(NO3)39 H2O. Get telesolutions structure type zeolite H-ZSM-5 with silicate module SiO2/Al2ABOUT3=55, SiO2/Fe2O3=550.

Then 70 g of JAS with silicate module SiO2/Al2ABOUT3=55, SiO2/Fe2ABOUT3=550 mix from 1.77 g of N3IN3with the volume of 34.12 g lO(HE) and subjected to mechanochemical treatment in a vibrating mill for 12 hours the resulting powder was formed into pellets or tablets, dried for 2-3 h at 20 or 30, then at 110 C for 3-4 h and calcined in air for 8 h at 550-600 C.

The obtained zeolite catalyst has a composition, wt.%:

Telesolutions 70

IN2O31

Al2ABOUT329

Example 5. 70 g JAS with silicate module SiO2/Al2O3=60, SiO2/Fe2O3=65 mixed with between 6.08 g of cu(NO3)23H2O, 1,77 g H3IN3, 31,76 g lO(HE) and subjected to mechanochemical treatment in a vibrating mill for 12 hours the resulting powder was molded, dried for 2-3 h at 20 or 30, then at 110 C for 3-4 h and calcined in air for 8 h at 550-600 C.

The obtained zeolite catalyst has a composition, wt.%:

Telesolutions 70

CuO 2< silicate module SiO2/Al2ABOUT3=60, SiO2/Fe2O3=65 take JAS with silicate module SiO2/Al2O3=55, SiO2/Fe2O3=550, wt.%:

Telesolutions 70

CuO 2

IN2O31

Al2ABOUT327

Example 7. 70 g JAS with silicate module SiO2/Al2ABOUT3=55, SiO2/Fe2O3=550 mix from 7.31 g of Zn(NO3)26H2O, 1,77 g H3IN3, 31,76 g lO(HE) and subjected to mechanochemical treatment in a vibrating mill for 8 hours the resulting powder was molded, dried for 2-3 h at 20 or 30, then at 110 C for 3-4 h and calcined in air for 8 h at 550 to 600 C.

The obtained zeolite catalyst has a composition, wt.%:

Telesolutions 70

ZnO 2

IN2ABOUT31

Al2O327

Example 8. In the same way as in example 7, but the catalyst was further treated with water vapor. For this zeolite-containing catalyst after calcination is loaded into the reactor and subjected to thermoprotei treatment with water vapor (100%) at 480, with a bulk velocity of water flow (liquid) 1 h-1during the 8 o'clock

Example 9. In the same way as in example 7, but instead 7,31 g Zn(NO3)2 6N2Oh, 1,77 g H3INTelesolutions 70

ZnO 5

P2O51

Al2ABOUT324

Example 10. In the same way as in example 7, but instead 7,31 g Zn(NO3)2 6N2About take the 3.65 g of Zn(NO3)26N2Oh and 4,27 g GA(NO3)28H2O.

The obtained zeolite catalyst has a composition, wt.%:

Telesolutions 70

ZnO 1

GA2About 1

IN2O31

Al2About 27

Example 11. In the same way as in example 10, but the catalyst was further treated with water vapor. For this zeolite-containing catalyst after calcination is loaded into the reactor and subjected to thermoprotei treatment with water vapor (100%) at 520 C, with a bulk velocity of water flow (liquid) 1 h-1within 4 hours

Example 12. In the same way as in example 7, but instead 7,31 g Zn(NO3)26N2Oh and 31,76 g lO(HE) take 0.55 g NH4Re4and 33,53 g lO(HE).

The obtained zeolite catalyst has a composition, wt.%:

Telesolutions 70

Re2O70,5

IN2ABOUT31

Al2ABOUT328,5

Example 13. In the same way as in example 7, but instead 7,31 g Zn(NO3)26N2About take 2,72 g (NH4)2MoO4<"ptx2">Moo32

IN2ABOUT31

Al2ABOUT327

Example 14. In the same way as in example 7, but instead 7,31 g Zn(NO3)26N2About take 8,53 g GA(NO3)28H2O.

The obtained zeolite catalyst has a composition, wt.%:

Telesolutions 70

GA2ABOUT32

IN2O31

Al2ABOUT327

Example 15. In the same way as in example 7, but instead 7,31 g Zn(NO3)2 6H2O take 5.32 g La(NO3)26N2O.

The obtained zeolite catalyst has a composition, wt.%:

Telesolutions 70

La2O32

IN2ABOUT31

Al2O327

The resulting catalysts are experiencing in the process of turning aliphati-ical hydrocarbons WITH2-C12(straight-run gasoline fraction 28-185 C) high-octane gasoline and/or aromatic hydrocarbons on the installation of flow-type fixed bed of the catalyst at temperatures of 350-550 C, space velocity of the raw material of 0.5 to 5.0 h-1and a pressure of 0.1 to 1.5 MPa.

In the process of converting a mixture of aliphatic hydrocarbons WITH2-C12(straight-run gasoline fraction 28-185 C) with increasing temperat reactions of cracking, dehydrogenation, isomerization, dehydrocyclization and paraffin aromatization of hydrocarbons from the formation mainly in the first stages of the process of olefinic hydrocarbons, which later turn into isoparaffin and alkylaromatic hydrocarbons. Introduction to telesolutions modifying additives from the group of copper, zinc, gallium, lanthanum, molybdenum, rhenium in an amount of 0.1-10.0 wt.% allows to considerably increase the output of high-octane gasoline and aromatic hydrocarbons from aliphatic hydrocarbons2-C12compared to the unmodified zeolite.

The table below shows examples clarify the invention without limiting it.

As can be seen from the examples of catalysts 1-16 table catalysts 3-15 have a higher output (60-78%) of liquid products of the reaction is high - octane gasoline from a mixture of aliphatic hydrocarbons WITH2-C12than the catalyst (example 16) prototype Pat. EN N 2165293.

Thus, the proposed catalysts for the conversion of aliphatic hydrocarbons2-C12in high-octane gasoline and/or aromatic hydrocarbons on the basis of zhelezohromovye with the structure of the high-type zeolite H-ZSM-5 with silna least one compound from the group of copper, zinc, gallium, lanthanum, molybdenum, rhenium or mixtures thereof in an amount of 0.1-10.0 wt.% allow to increase the output of high-octane gasoline to 60-78% and aromatic hydrocarbons up to 41-42% of aliphatic hydrocarbons WITH2-C12.

The proposed method allows to significantly simplify the technology of preparation of the catalyst in comparison with the existing methods due to the exclusion of several stages: the stage of precipitation of aluminum hydroxide, impregnation of the corresponding metal salts and others, as a consequence, there are no waste water and emissions.

Preliminary mechanical activation of a mixture of the starting components can significantly reduce the temperature of formation of the active components and to obtain highly dispersed, active and selective catalyst. Introduction metals modifier in an amount of 0.1-10.0 wt.% in telesolutions allows to increase the output of high-octane gasoline to 62-76% and aromatic hydrocarbons up to 41-42% of aliphatic hydrocarbons.

Method of producing high-octane gasoline and/or aromatic hydrocarbons from aliphatic hydrocarbons 2-C12in the presence of catalysts based on iron is B>3=20-160, SiO2/Fe2O3=30-5000 and modified at least one compound from the group of copper, zinc, gallium, lanthanum, molybdenum, rhenium in an amount of 0.1-10.0 wt.% allows to increase the output of high-octane gasoline and aromatic hydrocarbons from aliphatic hydrocarbons2-C12than in the presence of a catalyst (example 16) prototype Pat. EN N 2165293.

1. The catalyst for the conversion of aliphatic hydrocarbons2-C12in high-octane gasoline and/or aromatic hydrocarbons containing zeolite with structure of ZSM-5, the connecting component is aluminum oxide, the modifying component, characterized in that it contains telesolutions with silicate module SiO2/Al2O3= 20-160, SiO2/Fe2O3= 30-5000; as modifying component contains at least one oxide of an element selected from the group of copper, zinc, gallium, lanthanum, molybdenum, rhenium; as a hardening additive contains an oxide of boron, phosphorus, or mixtures thereof; a catalyst formed during the heat treatment and has the following composition, wt. % (based on oxide):

Telesolutions with silicate module

SiO2/Al2O3= 20-160 and their mixture 0,5-5,0

Alumina Rest

2. The method of producing catalyst under item 1, characterized in that telesolutions with the structure of zeolite ZSM-5 with silicate module SiO2/Al2O3= 20-160, SiO2/Fe2O3= 30-5000 get the hydrothermal crystallization of a reaction mixture at 120-180C for 1-6 days, containing sources of silicon oxide, aluminum oxide, iron oxide, oxide of alkali metal, and hexamethylenediamine were water, with further mixing zhelezohromovye with compounds of modifying metals, hardening additives and a binder, followed by mechanochemical processing, forming the catalyst mass, drying and calcining.

3. The method of producing catalyst according to p. 2, characterized in that the catalyst was prepared by dry mixing zhelezohromovye modifying metal compounds, hardening additives and a binder, followed by mechanochemical processing in a vibrating mill for 0.1 to 72 hours, by forming the catalyst mass, drying at 100-110S for 0.1-24 h and calcining at 550-600C) for 0.1-24 hours

4. The method of transformation of aliphatic hydrocarbons2-C12in high-octane gasoline and/or aromatic hydrocarbons in the presence of a catalyst, from the-FROM12in high-octane gasoline and/or aromatic hydrocarbons is carried out at 300 - 550C, flow rate of 0.5 to 5.0 h-1and a pressure of 0.1 to 1.5 MPa.

 

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