JPS62285986A - Production of intermediate fraction from isoparaffin and olefin - Google Patents

Abstract

PURPOSE:To product an 8-15C oil intermediate fraction from an isoparaffin and an olefin under mild reaction conditions, by the use of a solid superstrong acid catalyst containing a group VIII metal or a rare earth element. CONSTITUTION:A 4-6C isoparaffin and olefin are catalytically reacted with each other in the presence of the below-defined solid superstrong acid catalyst so as to be converted into an 8-15C hydrocarbon, thereby obtaining an oil intermediate fraction. The catalyst is obtd. by incorporating a group VIII metal or a rare earth metal in a carrier comprised of a hydroxide or oxide of a group IV metal and/or a hydroxide or oxide of a group III metal, then treating the formed catalyst precursor with a treating agent contg. sulfur ion and finally burning the treated catalyst for stabilization thereof. Examples of the group VIII metal include at least one member selected from among nickel, platinum, palladium, and rhodium. Examples of the rare earth elements include at least one member selected from among lanthanum, cerium, praseodymium, and neodymium. These metals and elements may be in a compound form with other elements.

Description

Detailed Description of the Invention 3 Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a method for producing petroleum middle distillates from isoparaffins and olefins. More specifically, carbon number 4-6
isoparaffins and olefins in the presence of a specific catalyst,
It relates to the above-mentioned method, which comprises converting it into a hydrocarbon having 10 to 15 carbon atoms by catalytic reaction.

[Conventional technology]

Light naphtha produced in the petroleum industry, i.e. boiling point approximately O
While there is a tendency for a surplus of C to approximately 100C fractions, kerosene,
Demand for heavy naphtha is strong.

Therefore, a technology for converting light naphtha into heavier hydrocarbons is desired.

On the other hand, as a technique for alkylating reaction between isoparaffins and olefins, a technique for producing alkylated gasoline using a liquid catalyst such as H2SO4 or HF is conventionally known.

However, from light naphtha (C4 to C6 baraffin) to C1
0""" There is no known technology for producing 15 petroleum middle distillates (kerosene and gas oil fractions), and as part of the effective use of light naphtha, we are developing a catalyst and method for producing petroleum middle distillates from light naphtha. is desired.

In addition, as solid acid catalysts for producing low-polymerized oligomers of olefins, ZSM-12 zeolite (%KAI No. 56-92222), crystalline aluminosilicate (
A super acid type zirconia catalyst (Japanese Patent Application Laid-open No. 6O-203695) is known; however, there is no research on catalysts for producing petroleum middle distillates using isoparaffins and olefins, and methods for producing such distillates. No reports are known.

However, there are examples of superacid zirconia catalysts being used for low polymerization reactions of pentene or hexene (JP-A No. 6 O-
205695), isoparaffins such as impentane and isohexane do not participate in the reaction and remain as unreacted aliphatic hydrocarbons.

[Problem that the invention seeks to solve]

As mentioned above, the present invention is a technology for converting light naphtha, which tends to be in surplus, into heavier hydrocarbons. The present invention provides a technology for grouping light naphtha containing olefins and olefins into heavy naphtha and kerosene fractions through alkylation and polymerization.

As mentioned above, although conventional superacid zirconia catalysts are capable of low polymerization of olefins such as pentene and hexene, they are inactive for isoparaffins such as impentane and isohexane. The present invention has developed a catalyst that can involve isoparaffins in the reaction, and selectively produces C+o'=C+s hydrocarbons, which are petroleum middle distillates, through the reaction between olefins and isoparaffins. Kerosene] It was designed to be used as a base material.

[Means for solving problems]

The present invention solves the above-mentioned problems by using a solid superacid type catalyst containing a sulfate group to which a group VIII metal or a rare earth element is added.

That is, the present invention combines isoparaffins and olefins having 4 to 6 carbon atoms with hydroxides or oxides of group II metals and/or
Or ■ A solid super acid type obtained by adding a group VIII metal or rare earth element to a carrier made of hydroxide or oxide of lacrimal gold, @, further treating it with a sulfuric acid radical-containing treatment agent, and stabilizing it by firing. The present invention relates to a method for producing petroleum middle distillates from isoparaffins and olefins, characterized by converting them into hydrocarbons having 10 to 15 carbon atoms through a catalytic reaction in the presence of a catalyst.

The middle distillates (C, . . . -C15) produced according to the present invention are obtained by a complex reaction of lower polymerization between olefins and alkylation of olefins and isoparaffins.

The raw materials used in the present invention are olefins having 4 to 5 carbon atoms and isoparaffins, and the lower the mixing ratio of olefins, the higher the yield of petroleum middle distillates can be produced.

As a raw material source, isoparaffin is derived from light naphtha (mainly
Olefins can be produced by isomerizing light naphtha with a known chromia-alumina catalyst. Industrially, it is possible to utilize isoparaffins and olefins such as butane and butene, which are produced as by-products during catalytic reforming and catalytic cracking in the petrochemical industry.

The catalyst used in the present invention is disclosed in Japanese Patent Application No. 59-188206.
No., % Application No. 188207, 1982, Patent Application No. 1882-273, 1983
48j, Japanese Patent Application No. 1) i359-273482, and Japanese Patent Application No. 60-58229. This catalyst contains a Yllll group metal or a rare earth element, and a support consisting of a hydroxide or oxide of a Y group metal and/or a hydroxide or oxide of a Group I metal is treated with a sulfate group-containing treatment agent. It is a solid acid catalyst obtained by performing calcination and stabilization.

The above-mentioned apical group metal hydroxides or oxides include at least 1fi selected from aluminum, gallium, osmium, and thallium, and the group IV metal hydroxides or oxides include titanium, zirconium, hafnium, silicon, and kermanium. , at least one selected from tin
Preference is given to using metal hydroxides or oxides. In addition, the Group VIII metal is at least one selected from nickel, platinum, ruthenium, rhodium, palladium, osmium, and iridium, and the rare earth elements are lanthanum, cerium, praseodymium, neodymium,
At least one selected from samarium and gadolinium
Preferably, metals or their compounds are used.

Furthermore, as the sulfate group-containing treatment agent, at least one sulfate group-containing substance or sulfate group precursor selected from sulfuric acid, ammonium sulfate, ammonium sulfite, ammonium hydrogen sulfate, sulf7lyl chloride, heptanosulfonic acid, and thionyl chloride. Substances are preferably used. Also, firing stabilization [,45
Preferably, it is carried out at a temperature of 0-aooC.

The reason for adding Group VIII metals or rare earth elements to this catalyst is that the Group II metals or rare earth elements act as the center of reaction active sites in contrast to the solid strong acid sites formed by the sulfuric acid group and the surface of the metal acid A and arsenic. , Promoting the addition of protons to olefins by a carbonium ion mechanism, causing the alkylation reaction and the first nogomerization reaction to occur simultaneously, and selectively producing a C10''15 petroleum middle distillate.Furthermore, (1) It has been found that the addition of Group 11 metals or rare earth elements is effective in improving catalyst life and suppressing side reactions (decomposition reactions, isomerization reactions, polymerization reactions of tetramers or more).

As mentioned above, the present invention is directed to middle distillates, that is, C1° to C15.
It is characterized in that it primarily produces hydrocarbons, and in doing so, suppresses the formation of larger polymers and coke formation. In order to produce the hydrocarbons, the temperature of the reaction system and the method of injecting the raw materials are important factors.

That is, the reaction temperature is usually room temperature to about 90C. A high temperature of 1000° C. or more is not a good idea because a decomposition reaction occurs and the desired hydrocarbon yield decreases. Further, as for the raw material, it is desirable that a mixed gas of isoparaffin and olefin be fed onto the catalyst at the same time. This is because if you send isoparaffins first and olefins later,
This is because only the alkylation reaction occurs selectively, and conversely, when the olefin is fed first and the isoparaffin is fed later, the polymerization reaction occurs selectively.

Further, the catalyst used in the present invention is a solid super strong acid, and if the catalyst is left in the air, a large amount of water will be completely adsorbed and the acid strength will be significantly reduced. Therefore, in order to remove moisture etc. from the catalyst, it is desirable to pre-treat the catalyst by heating it at 300C for 30 minutes. After this pretreatment, it is evacuated and the raw material is injected.

Note that the reaction between isoparaffins and olefins in the present invention is a seed type reaction using an autoclave reactor, and the p1 catalyst and the raw material are brought into contact in a solid-liquid state. Therefore, the reaction pressure has little effect on the carbon number distribution of this reaction product,
Normally, this may be carried out under conditions such that the pressure indicated on the gauge is equal to the pressure of the vapor of the raw material.

[Effect]

According to the present invention described above, a petroleum middle distillate having a carbon number of 10 to 15 can be produced from isoparaffins and olefins under mild reaction conditions by using a solid super acid type catalyst containing group metals or rare earth elements. It becomes possible to do so.

〔Example〕

Catalyst Preparation Example 1 (Catalyst of the Invention) Commercially available zirconium oxychloride (manufactured by Kanto Kagaku) 90.9 was dissolved in 700 g of pure water, and an appropriate amount of aqueous ammonia was added to adjust the pH to 110 to form a precipitate. This precipitate was aged for a day and night, filtered, washed and dried, and Zr(OH)4
A white powder of 5aid was obtained. This white powder was impregnated in a chloroplatinic acid aqueous solution (concentration such that the amount was 0.5 parts by weight in terms of platinum metal per 100 parts by weight of the carrier).
After drying at 0C for a day and night, this powder was introduced into a 250M 1NH2SO4 solution, dried at 110C for a day and night, and then calcined at 600C for 3 hours to obtain catalyst A.

Catalyst Preparation Example 2 (Catalyst of the Invention) Zr(OH)4 powder prepared by the same method as Preparation Example 1. p was introduced into 100 cc of I N H2So4 and dried at 110C for a day and a night. The obtained powder was impregnated in a palladium chloride aqueous solution, a nickel nitrate aqueous solution, and a lanthanum nitrate aqueous solution, respectively, dried, and then calcined at 600 C for 3 hours to obtain catalysts BXC and D.

Catalyst Preparation Example 3 (Catalyst of the Present Invention) Aluminum chloride (manufactured by Wako Tsumugi Pharmaceutical Co., Ltd.) 100.9% pure water 80%
Pl″I by dissolving it in Pl″I and adding an appropriate amount of ammonia.
(IL-10, precipitate was generated, filtered with air and dried to obtain 30.9% of white powder of &l!(OH)3. On the other hand, it was impregnated with a concentration of 1.0 parts by weight calculated as platinum metal, and after drying at 110C, j N H2So4
The mixture was introduced into 500 cc of solution, dried at 110C for a day and night, and then calcined at 600C for 3 hours to obtain catalyst x'6.

Catalyst Preparation Example 4 (Catalyst of the Invention) Z r (OH) prepared by the same method as Preparation Example 1
4 powder 10.9 was added to a lanthanum nitrate aqueous solution (carrier weight 1 (1
After drying at 110C, the solution was introduced into a sulfonyl chloride solution, a fluorinated sulfonic acid solution, and an ammonium sulfate aqueous solution. After drying at 110C for a day and night, the catalysts were calcined at 600C for 3 hours to obtain catalysts F, G, and Hi.

Catalyst Preparation Example 5 (Comparative Catalyst) After drying 20.9 kg of Zr(OH)4 powder by the same method as in Preparation Example 1 at 110C for a day and night, this powder was introduced into a 1NH2So4 solution, and after drying at 110C for a day and night. ,6
A catalyst product was obtained by firing at 00C for 3 hours.

Catalyst Preparation Example 6 (Catalyst of the Invention) Each powder 101 of gallium oxide, indium oxide, thallium oxide, titanium oxide, hafnium oxide, silicon dioxide, germanium oxide, and tin oxide was mixed with an aqueous solution of chloroplatinic acid (based on 100 parts by weight of the carrier, After drying at 110C for a day and night, the solution was introduced into 100cc of 1N H2So4 solution.
After drying at 110C for a day and night, it was calcined at 600C for 3 hours to obtain catalysts J, L, M, , N, O, Pl Q.

Catalyst Preparation Example 7 (Catalyst of the Invention) Zr (O) () prepared in the same manner as Preparation Example 1
4 powder 10. p was introduced into 1NH2S04100CC and dried at 110C all day and night. The obtained powder was impregnated into aqueous solutions of ruthenium chloride, rhodium chloride, osmium chloride, iridium chloride, cerium nitrate, praseodymium chloride, neodymium nitrate, samarium nitrate, and gadolinium nitrate, dried, and then calcined at 600C for 3 hours to prepare the catalyst. R,S
, T, υ, v, w, x, y, z were obtained.

Catalysts A to 2 obtained in Examples were all tested using Hammett's reagent with acid strength (
Ho)<-f 3.5'i, and it was found to be a solid super strong acid type catalyst. A reaction test for producing petroleum middle distillates from isoparaffins and olefins using these prototype catalysts was conducted in the following manner.

First, an experimentally prepared catalyst is charged into an autoclave reaction experiment apparatus, and heated and exhausted at 300 C for 30 minutes as a pretreatment. After cooling, the autoclave reaction experiment apparatus was immersed in a dry ice-methanol solution to obtain 1-butane/cis-
A predetermined amount of 2-butene mixed gas is introduced into a cooled autoclave reaction experiment apparatus. After the reaction was carried out at a predetermined temperature, a predetermined stirring number, and a predetermined time, the composition of the reaction product was analyzed by gas chromatography, and the coke-like substance adhering to the catalyst was measured by a coke analyzer. Raw material is 1-butane/
Using cjg -2-butene mixed gas, 1-butane/
The mixing ratio of cig-2-butene was 10, and the number of stirring was 1.
The speed was set at 60 rpm.

The test results are shown in Table 1.

Conversion of olefin (%) = cis-2-butene (vrtX) in the raw material 2-7'?71wt C15 hydrocarbons are selectively produced in large amounts, and the C5 selectivity is also high, so middle distillates (C
,. ~C15) can be produced.

〔Effect of the invention〕

According to the present invention, a C10-15 petroleum middle distillate can be produced in high yield from isobacin and olefins under mild reaction conditions, and contains isoparaffins and olefins that are in low demand and tend to be in surplus. It is industrially useful as a method of obtaining heavier naphtha, which is in great demand, from light naphtha.

Among the sub-agents: 1) Akira Sub-agent Ryo Hagi Hara - Sub-agent Atsuo Annishi

Claims (1)

[Claims] 1. Isoparaffins and olefins having 4 to 6 carbon atoms, I
A support made of a hydroxide or oxide of a group V metal and/or a hydroxide or oxide of a group III metal contains a group VIII metal or a rare earth element, and is further treated with a sulfuric acid radical-containing treatment agent, A method for producing petroleum middle distillates from isoparaffins and olefins, characterized by converting them into hydrocarbons having 10 to 15 carbon atoms through a catalytic reaction in the presence of a solid super acid type catalyst obtained by stabilization by calcination. . 2. Group III metal hydroxide or oxide is aluminum, gallium, indium, thallium, Group IV metal hydroxide or oxide is titanium, zirconium, hafnium,
The method for producing a petroleum middle distillate according to claim 1, characterized in that the metal hydroxide or oxide is at least one metal hydroxide or oxide selected from silicon, germanium, and tin. 3. The Group VIII metal is nickel, platinum, ruthenium, rhodium, palladium, osmium, iridium, and the rare earth element is at least one metal selected from lanthanum, cerium, praseodymium, neodymium, samarium, and gadolinium, or a compound thereof. A method for producing a petroleum middle distillate according to claim 1 or 2. 4. The sulfate group-containing treatment agent is at least one selected from the group of sulfate groups or sulfate group precursors consisting of sulfuric acid, ammonium sulfate, ammonium sulfite, ammonium hydrogen sulfate, sulfuryl chloride, fluorinated sulfonic acid, and thionyl chloride.
Claims 1 to 2 are characterized in that they are seed substances.
A method for producing a petroleum middle distillate according to any of Item 3. 5. A method for producing a petroleum middle distillate according to any one of claims 1 to 4, characterized in that the calcination stabilization is carried out at a temperature of 450 to 800°C.