JPH0490854A - Solid crystalline phosphoric acid to hydrocarbon conversion catalyst - Google Patents

Abstract

PURPOSE: To prepare a solid crystalline phosphoric acid catalyst useful for hydrocarbon inversion by crystallizing silicon phosphate and silicon pyrophosphate together with siliceous raw materials under a specific steam level and temperature condition. CONSTITUTION: Phosphate oxides comprising crystals of both silicon phosphate and silicon pyrophosphate, and siliceous raw materials such as diatomite or the like are used. A mixture of these are crystallized at a temperature of 250 to 450 deg.C and the steam concentration of 3 to 50 mole % of all steam necessary in the crystallization process. Obtained thereupon is a solid crystalline phosphate catalyst having a desired phosphate catalyst crystal and total silicon phosphate X-ray strength of 30% or more higher than alpha-alumina. The solid phosphate catalyst thus obtained is useful for hydrocarbon inversion such as aromatic alkyl, polymerization of olefin or the like.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is an improvement in which the total silicon phosphate X-ray intensity is 30% or more compared to alpha alumina, and it is composed of both silicon orthophosphate and silicon pyrophosphate crystals. The present invention relates to a solid crystalline phosphoric acid catalyst. This catalyst is particularly useful for hydrocarbon conversion.

BACKGROUND OF THE INVENTION Solid phosphoric acid is known to be useful in various hydrocarbon conversions, such as aromatic alkylation and olefin polymerization. The catalyst is a composition in which a catalytically active acid moiety is attached to a support or substrate. The substrate is primarily silicon orthophosphate, Si, (PO4), believed to be formed by a silica-phosphoric acid reaction.

Silicon pyrophosphate SiP, O, and derivatives thereof. This catalyst is primarily produced by extruding and deflagrating a mixture of silica and phosphoric acid. This reaction is simply shown below.

3 Sin, + 4 H, PO4→ Si, (PO
, ), + 6 H, 03in, + 2 H, PO,
→ SiP, O, +3) 1.0 In the above reaction, phosphoric acid reacts well with silica, and a phosphate shape is produced depending on the stoichiometry and reaction conditions. Silicon orthophosphate dehydrates during drying to obtain silicon pyrophosphate, and this is believed to be one mechanism for silicon pyrophosphate formation.

The conversion of silicon ortho-to-billow also depends on factors such as temperature and water addition, and is illustrated by the following reaction equation.

Si, (PO,), + 2 H, PO, → 3Si
P, O, + 3H O81, (PO,), 10 heating →
2SiP, O, +SiO.

These reactions were used in the preparation of more complex catalysts.

Low activity or low stability catalysts are the result of low crystallization caused by the low crystallization conditions of prior art processes. It has been observed that the stability of these catalysts used for hydrocarbon conversion is significantly improved by relatively high degree of crystallization control.

Methods that utilize solid phosphoric acid catalysts and their physical properties, such as their crushing power, are known in the prior art. It is not known to improve the stability of hydrocarbon applications by maximizing total silicon phosphate crystals. And that is the subject of the present invention.

U.S. Pat. No. 2,650,201 discloses deflagrating solid phosphoric acid by adding a hydrolyzable compound of a metal selected from the group consisting of titanium, zirconium, and tin to a composite of metals containing a predeflagrated solid phosphoric acid catalyst. A method for improving the structural strength of acid catalysts is described. The preferred explosion temperature ranges from ioo' to 500°C.

The catalyst of the present invention does not add any metal and has a 2.650,
No. 201 differs in that it does not describe the benefit of maximizing silicon phosphate crystals.

U.S. Pat. No. 3,112,350 describes a process for polymerizing hydrocarbon olefins in the presence of a special solid phosphoric acid catalyst. This special catalyst has high P for Sin,
O, in a molar proportion of about 1.08 or more. The catalyst also preferably needs to be exploded at a temperature of about 560°C. This 3,112,350 is about 560℃ to achieve a special crystal ratio of about 28:1 of C type crystal and B type crystal.
teaches the benefits of smoking catalysts. however,
When the molar ratio of P2O, to Si starvation exceeds 1.08, silicon pyrophosphate (SiP,O,

It is considered that only raw materials with a higher content of phosphate than P, O, /SiO, = 1) can be used. Silicon orthophosphate (Si, (PO,), ) is P,
Since 0JSiO, is 0.75, it is considered that it cannot be used. 3.1] No. 2,350 discloses considering the crystalline fraction of the catalyst based on the most effective conditions of implementation, but does not provide details of requiring overall crystallinity.

U.S. Pat. No. 3,673,111 discloses a method for preparing solid phosphoric acid catalysts by two-step roasting to improve the physical strength of the catalyst. High crushing strength is achieved by exposing the unfinished catalyst to steam at temperatures between 260° and 460° C. followed by a second deflagration in the absence of steam.

US Pat. No. 4,52], 638 describes the use of solid phosphoric acid catalysts in the production of tertiary olefins. A useful catalyst for this process is 500°C in an inert atmosphere.
The temperature is preferably about 600°C, particularly preferably about 700°C.
Deflagrates above ℃. If the roasting temperature is below 500°C, a catalyst with sufficient activity and long life cannot be obtained (column 4, line 63 to column 5, line 2). The difference between this and the present invention is that the highly stable solid phosphoric acid catalyst is deflagrated at a temperature below 450° C., thereby achieving a certain degree of improvement in the overall silicon-based sulfate crystal.

[Means to solve the problem]

It has been found that improved catalyst stability in catalytic condensation reactions is achieved by maximizing the overall and crystalline morphology contained in the solid phosphoric acid catalyst. Furthermore, this highly crystalline silicon phosphate product is obtained in a manner that strictly controls water vapor levels and temperature during the crystallization process.

The main object of the present invention is to provide an improved solid phosphoric acid catalyst. The improved catalyst has a longer catalyst life due to improved catalyst crystallinity and crystallinity.

Accordingly, a broad aspect of the invention is a solid crystalline phosphoric acid catalyst. The solid crystalline phosphoric acid catalyst is characterized in that the total silicon phosphate X-ray intensity is 30% or more compared to alpha alumina. The solid phosphoric acid catalyst is further characterized in that it contains crystals of both silicon orthophosphate and silicon pyrophosphate. The desired crystallinity is obtained by crystallizing an amorphous mixture of phosphorus oxide and silicic raw material under controlled conditions. Crystallization of the catalyst is most effectively carried out by using a crystallization process in which the temperature of one or more crystallization zones is between 2506 and 450°C and 3 to 50 mole percent water vapor based on the total vapor in the crystallization zone. .

In a narrow embodiment, the solid crystalline phosphate catalyst has a total silicon phosphate X-ray intensity of greater than 40 percent relative to alpha alumina due to the combination of silicon pyrophosphate beak (002) and silicon orthophosphate beak (113) and Phosphate alpha alumina external standards (012), (104)
and (113) The solid phosphoric acid catalyst contains at least 0.1 percent X-
Silicon pyrophosphate with line strength and at least 30
It is made of silicon orthophosphate with a percent X-ray intensity (both relative to alpha-alumina). Desired phosphoric acid crystallinity is obtained by preparing an amorphous mixture of phosphorus oxide and silicic raw material at a temperature of 3506 to 450°C in one or more crystallization zones, based on the vapor during the crystallization process. 20 mole percent water vapor
It is produced by crystallization for a total time of from 120 minutes to 120 minutes or more.

Solid phosphoric acid catalysts are well known for their utility in a variety of important hydrocarbon conversion processes.

However, the use of solid phosphoric acid catalysts in such processes is always accompanied by problems such as catalyst activity, catalyst decomposition, catalyst strength, and catalyst life. Therefore, methods for producing active, strong catalysts are always being sought. To this end, long-lived catalyst formation was discovered.

The main and active component of the solid catalyst thus envisaged is an acid of phosphorus, preferred being the +5 valence of phosphorus.

The acid should be from about 60 to about 80 weight percent of the final produced catalyst mixture, preferably greater than 80 weight percent.

The various acids of phosphorus, orthophosphoric acid (H, PO, ) and birophosphoric acid (84 P, O, Any other phosphorous acids may be used provided they are not limited to use. However, when different phosphorous acids are used to produce catalysts that carry out the same organic reaction, there is no intention to discuss slight differences in processing means due to the different acids.

However, it is believed that catalysts made with the crystallization characteristics disclosed herein have superior hydrocarbon conversion compared to catalysts made with different processes and similar precursors.

When orthophosphoric acid is used as the first component, different concentrations of the aqueous solution from about 75 to 100 percent are used; acids containing some free phosphorus pentoxide can also be used. The orthoacid can contain the exact percentage of pyroic acid that corresponds to the first stage of dehydration of the orthophosphoric acid. Within these concentration ranges, acids provide liquids of varying viscosities and are easily mixed with the wicking material. In practice, birophosphoric acid corresponding to 2〇, P, O, is mixed with a silicate raw material at a temperature slightly higher than its melting point (61° C.) and heated to obtain a pyroic acid adsorbent mixture. This is different from when ortho acids are used.

triphosphate formula) 1. P, 0. , and is used as a starting material in the method for producing the catalyst of the present invention. These catalyst compositions may be prepared from the siliceous raw materials described herein and phosphoric acid mixtures including orthophosphoric acid, birophosphoric acid, triphosphoric acid, and other polyphosphoric acids.

There are two classes of materials used as adsorbents or carriers for phosphorus oxides. The first are materials with excellent siliceous properties, including diatomaceous earth and synthetic porous silica. The second set of materials may be used alone or in combination with the first set of materials and generally includes members of the alumina-silicate group and various filled earths and clays such as bentonite, montmorionite, acid-treated clays, etc. Contains natural products.

In preparing the catalyst mixture utilized in the present invention, the phosphorus oxyacid and the siliceous raw material are mixed at a temperature of about 10' to about 232'C, preferably about 95' to 180'C to form the mixture. Form.

In this way, satisfactory results are obtained with polyphosphoric acid (82% p,
o, containing) to a temperature of about 170° C. and then mixing this hot acid with diatomaceous earth. Polyphosphoric acid and diatomaceous earth are a hybrid in which the weight ratio of phosphorus pentoxide to diatomaceous earth is from about 1.8:l to about 6=1. The mixture is superficially slightly moist and almost dry, but when pressure is applied with a hydraulic or spiral extruder, it becomes plastic and the mixture is formed into flakes and cut into granules. This amorphous extrudate is later crystallized to produce a final catalyst with desired properties.

Crystallization of the amorphous extrudates is accomplished by controlling temperature, steam rate, and time techniques in known crystallization processes and known equipment. The temperature conditions, water vapor addition rate and crystallizer time conditions directly affect the final form and amount of crystals in the finished solid phosphoric acid catalyst. The finished solid phosphoric acid catalyst has a total silicon phosphate X-ray intensity of at least 30 percent relative to alpha alumina standards and is comprised of both silicon orthophosphate and silicon pyrophosphate crystals.

The term "crystallization" refers to the apparatus or process as used in this application and the temperature control, steam rate and time in the apparatus to provide the desired crystallinity of the solid phosphoric acid catalyst of the present invention. devices belong to this category.

In particular, such a crystallization device is an oven or a furnace. Typical of such equipment are those known in the art, such as pinewood ovens or furnaces, kilns, and batch or continuous deflagration. Crystallization can be carried out batchwise or continuously. Such crystallization methods depend on temperature,
It can include 1 or more zones in which water vapor can be controlled for a period of time.

Temperature is the first critical crystallization condition. Temperature is important both in dehydration of amorphous materials and in controlling the type of crystalline product resulting from the crystallization process. High temperatures, especially around 50
At 0° C. or higher, the solid phosphoric acid catalyst becomes substantially composed only of silicon pyrophosphate crystals. In order to obtain the desired catalyst with both silicon orthophosphate and silicon pyrophosphate crystals, the crystallization temperature range was increased to 250°.
It has been determined that temperatures between 350° and 450°C are most desirable, particularly between 350° and 450°C.

It is also an important aspect of the invention that, in conjunction with the particular crystallization temperature, the content of water vapor or humidity during the crystallization process is tightly controlled so that the catalyst obtains the desired crystallinity. The water vapor content in the steam of the crystallization process is based on the total steam content of the crystallization zone.
and 50 mole percent. , i & also preferred water vapor is 5 to 30 mole percent based on the total vapor in the crystalline region. Control of the water vapor content in the crystallization zone does not require steam to be supplied from an external source. Much of the water vapor is present in the vapor in the crystallization zone due to evaporation of water from the catalyst during crystallization. The addition of water vapor to the crystallization zone is when it is necessary to control the water vapor in the crystallization zone by varying the temperature and moisture content of the fresh catalyst throughout the crystallization zone.

The time of the crystallization process is also important. Typical total crystallization time is 2
Varies from 0 to 120 minutes or more. If more than one crystallization zone is used, the total crystallization time can be varied in placement, such as in the range of 20 to 120 minutes.

A further preferred aspect of the invention is that if there is more than one crystalline zone, at least one crystalline zone must be operated under steam conditions. More preferably, the terminal or final crystallization zone in the multi-step crystallization process is operated under the desired process conditions. The desired temperature range is typically the highest crystallization temperature. It is at this temperature and steam condition that manipulation of the terminal crystalline zone is theoretically most effective in rendering all of the catalyst crystalline and crystalline. This is not to say that other crystal regions next to the terminal region cannot be operated under favorable conditions. It is believed that this is the most efficient method of catalyst production described herein.

The solid phosphoric acid catalyst prepared by the above method has a total silicon phosphate X-ray intensity of 30 percent or more, preferably 40 percent or more, compared to an alpha-alumina standard. The catalyst is also preferably a silicon pyrophosphate having an X-ray intensity of at least 1 percent compared to alpha alumina and preferably at least 30 percent x-ray intensity compared to alpha alumina.
It is made of silicon orthophosphate with a percent X-ray intensity.

The crystal form and crystallinity of the completed solid phosphoric acid catalyst were determined by X-
I decided on line diffraction. This analysis provides comparative values for alpha alumina of both silicon orthophosphate and silicon pyrophosphate, each relative to each other and not absolute values of crystallinity.

Comparative crystallinity determination of completed solid phosphoric acid catalyst samples was
The sample is first ground to a fine powder (less than 44 microns in size). The sample is then exposed to an X-ray tube, preferably equipped with a copper anode X-ray tube.
Obtain a quantity of line diffraction scan. The raw integrated intensity of the silicon phosphate phase is the peak of silicon pyrophosphate (0
02) and silicon orthophosphate peak (113)
) supplied by What is obtained is also (012),
The relative X-ray intensity of the 6 silicon phosphate phase is the raw total intensity of the alpha-alumina external standard by combining the (104) and (+13) peaks. is obtained by dividing the raw total intensity of each of them by the sum of the intensities. The result is multiplied by 100 and expressed in percentages.

The X-ray diffraction results reported herein are expressed in terms of values such as total comparative crystallinity, silicon orthophosphate crystallinity, and silicon pyrophosphate crystallinity, and ultimately relative intensity percentages.

Total relative crystallinity is synonymous with total crystallinity.

The total crystallinity of the solid phosphoric acid catalyst is the sum of the crystallinity of silicon orthophosphate to alpha alumina and the crystallinity of silicon pyrophosphate to alpha alumina.

The relative strength ratio is the ratio of silicon orthophosphate crystallinity to alpha alumina divided by silicon pyrophosphate to alpha alumina.

The catalysts of this invention are useful in catalytic condensation, aromatic alkylation, and other types of hydrocarbon conversion processes. When used in the addition of olefinic hydrocarbons to polymers, the catalyst is formed as described above and used as a granular bed in a heated reactor, generally made of steel and through which the preheated hydrocarbon is fed. As such, the solid catalyst of the present process can be effectively used to polymerize olefin process mixtures containing hydrocarbon vapors, but the same catalyst can also be used to polymerize olefinic hydrocarbon polymers such as butylene. Gasoline can be produced by maintaining the liquid state under appropriate conditions during the oxidation process. When used in the polymerization of gaseous olefins in general, the catalyst particles formed are charged into an upright tubular treatment column and the olefin-containing gas mixture is passed down thereto at a temperature of about 140" to 290" and about 6. Passing at a pressure of 8 to about 102 atmospheres. These conditions are appropriate when processing olefin-containing feedstocks containing about 10 to 50 percent propylene and butylene. The catalyst is effective at temperatures of about 40° to about 250°C and pressures of about 34 to 102 atmospheres.

When used in the alkylation of aromatic hydrocarbons, the catalyst of the invention is placed in a tubular reactor or catalyst bed.

The preferred temperature for aromatic alkylation with the catalysts of this invention is the temperature of the initial reaction between the aromatic substrate and the particular olefin used to selectively produce the desired monoalkyl aromatic compound.

Generally, the preferred temperatures used are about 100° to 390°
℃, particularly from about 150'' to about 275°C.

The preferred pressure used herein is about 1 atmosphere or more, but about 1
Do not exceed 30 atmospheres. A particularly desirable pressure range is from about 10 to about 40 atmospheres at a flow rate of aromatic feedstock of 0.1 to about 50 hr-', particularly about 0.5 to 5 hr-'. It should be noted that the combination of pressures is an alkylation reaction in the liquid phase. In essentially liquid phase alkyl aromatic production processes, the catalyst is always washed with reactants, so that no precursors are deposited on the catalyst. Prevents cake build-up and reduces the amount of hydrocarbons that build up on the catalyst, increasing catalyst circulation life compared to gas phase alkylation processes where cake formation and reduced catalyst reactivity are major problems. be done.

"Essentially liquid phase" means that all of the active reactants are in the liquid phase.
However, there may also be inert compounds present in the gas phase, such as light olefins.

During use of this catalyst in a hydrocarbon conversion process, it is often advantageous to add small amounts of water to prevent excessive dehydration and thereby increase catalyst activity and substantially prevent water from the catalyst. Water or steam is added to the feed hydrocarbon to essentially balance the moisture content of the catalyst. The amount of water vapor is from about 0.1 to about 6.0 percent by volume of the organic feedstock fed.

The following examples illustrate the method of the invention and are not intended to limit the scope of the invention as claimed herein.

〔Example〕

Example I This example shows a general procedure for preparing amorphous phosphoric acid catalyst extrudates, which are converted to crystalline forms of solid phosphoric acid catalysts by various crystallization methods in the following examples.

Diatomaceous earth and P, 0. 85 percent or more of phosphoric acid is blended in a weight ratio of 1:2 at a temperature of 170°C. This raw material is extruded through the extruder to produce an extrudate with a diameter of about 5 mm. Amorphous properties were detected by X-ray of the fresh extrudates. The extrudates thus produced are later used in the crystallization examples described in Examples 1 to 2. The crystallinity of the finished catalyst was determined by X-ray diffraction. Standard X-ray diffraction techniques use N as a reference material.
A method using BS alpha alumina was used (see exact test method specification). Therefore, the crystallinity values of orthophosphate and pyrophosphate listed in the following examples are not absolute values but relative values of alpha alumina.

EXAMPLE ■ A batch of fresh amorphous solid phosphoric acid extrudate from Example 1 was subjected to a crystallization process in a small oven in 100-150 gram batches.

The oven strictly controls oven temperature and adds air and steam in equal, defined proportions. After about 20 minutes at 3 percent steam at an oven temperature of 250° C., the crystals were removed and crystallinity was detected. Crystalline silicon orthophosphate only has a 10% reduction compared to alpha alumina standard.
．． An X-ray intensity of 7% was detected.

No crystalline silicon pyrophosphate was detected.

Example M A batch of freshly made amorphous solid phosphoric acid extrudates from Example I was subjected to a crystallization process in a small oven similar to Example I. After approximately 20 minutes at an oven temperature of 250° C. and a 22 percent steam level, the catalyst was removed and analyzed for crystallinity. Only the crystalline form of silicon orthophosphate detected a relative X-ray intensity of 6.4 percent compared to the alpha alumina standard.

The results of this example and the results of Example ① show that water vapor is 250
It is shown that there is no effect on the production of crystalline silicon pyrophosphate below ℃.

Example ■ A batch of freshly made amorphous solid phosphoric acid extrudates from Example 1 was subjected to a crystallization process in a small oven similar to Example]. After approximately 50 minutes at an oven temperature of 392° C. and a 3 percent steam level, the catalyst was removed and analyzed for crystallinity.

Only the crystalline form of silicon orthophosphate detected a relative X-ray intensity of 44.9 percent compared to the alpha alumina standard.

Example V A portion of the crystalline solid phosphoric acid catalyst from Example 1 was subjected to further reprocessing in a small oven similar to Example 2 with 26 percent steam at 392° C. after 20 minutes. This additional treatment has a relative intensity ratio of silicon orthophosphate to silicon pyrophosphate of 4.4 compared to an all-silicon phosphate X-ray alpha-alumina standard with a 7.1:l ratio.
It decreased to 17 percent. This example shows that both steam and temperature are critical factors in the production of solid phosphoric acid catalysts having both ortho and pyrophosphate crystals.

Example ■ A batch of freshly made amorphous solid phosphoric acid extrudates from Example I was subjected to a crystallization process in a small oven similar to Example ■. After approximately 50 minutes in 18 percent steam at an oven temperature of 392° C., the catalyst was removed and analyzed for crystallinity.

The crystallinity of both silicon orthophosphate and silicon pyrophosphate detected a total X-ray intensity of 40 percent compared to the alpha alumina standard. The relative strength ratio between silicon orthophosphate and silicon pyrophosphate was 17.2:1.

Example ■ A portion of the crystalline solid phosphoric acid catalyst from Example ■ was further reprocessed with 3 percent steam for an additional 20 minutes at 392° C. in a small oven similar to Example ■. This additional treatment reduced the total silicon phosphate X-ray intensity relative to the alpha-alumina standard to 38.0 percent, while the relative intensity ratio between silicon orthophosphate and silicon pyrophosphate decreased to 12.7:1. did.

Example ■ A batch of freshly made amorphous solid phosphoric acid extrusions from Example I was subjected to a crystallization process in a small oven similar to Example ■. After approximately 70 minutes in 27 bas steam at an oven temperature of 430°C, the catalyst was removed and analyzed for crystallinity. The crystalline forms of both silicon orthophosphate and silicon pyrophosphate were detected at an intensity of 47.7 percent relative to the total X-ray alpha alumina standard.

The relative strength ratio between silicon orthophosphate and silicon pyrophosphate was 12.3:1.

EXAMPLE ■ Solid phosphoric acid catalysts prepared in essentially the same manner as described in Example ■ and completed under various deflagration conditions were prepared using silicon orthophosphate and silicon pyrophosphate
-Analyzed by line intensity. The results of this analysis can be shown in Table 1 below.

The analyzed catalyst was later used as a catalyst in an olefin polymerization process plant to test the catalyst life. The test was conducted at a pressure of approximately 68 atmospheres and a pressure of 1.8-2. The polyethylene feedstock was introduced at a liquid hourly rate of 1hr and a temperature of 149° to 230°C.

This test was in a conversion plant for commercial product production.

The comparison of the total crystallinity value, that is, the relative total X-ray intensity value and the catalyst life in Table 1, which shows the solid phosphoric acid catalyst test results in the blank space below, shows that the total crystallinity is directly related to the stability of the catalyst. It is inferred from the lifetime of the catalyst during the olefin polymerization process that the greater the total silicon phosphate relative X-ray intensity of the solid phosphoric acid catalyst, the more stable the solid phosphoric acid catalyst is.

[Brief explanation of the drawing]

The figure shows the conversion to 8.34 x 10 gal/lb of hydrocarbons in process per bond of solid phosphoric acid catalyst.
Figure 2 is a graphical representation of the catalyst properties related to the total crystallinity of the catalyst at -''rd/kg). A propylene condensation reaction was used to obtain catalyst lifetime data.

Claims (1)

[Claims] 1. An amorphous mixture of a phosphorus oxide and a silicic material consisting of crystals of both silicon orthophosphate and silicon pyrophosphate at a temperature of 250° to 450°C,
A solid having a total silicon phosphate X-ray intensity of 30% or more compared to alpha alumina having desired phosphoric acid catalyst crystals produced by a crystallization operation at a water vapor concentration of 3 to 50 mole percent of the total vapor in the crystallization step. Crystalline phosphoric acid catalyst. 2. The solid crystalline phosphoric acid catalyst according to claim 1, wherein the catalyst crystallizes in a total time of 20 to 120 minutes or more. 3. Total silicon phosphate X-ray intensity is 40% or more compared to alpha alumina, silicon pyrophosphate crystals exhibit at least 1.0% X-ray intensity, and silicon orthophosphate crystals exhibit at least 30% It appears that both are for alpha alumina, and that the desired phosphoric acid catalyst crystals are prepared by preparing an amorphous mixture of phosphorus oxide and silicic acid raw material at a temperature of 350° to 450° C. in an amount of 5 to 30 mole percent of the total gas of the crystallization process. Claim 1, characterized in that it is produced by crystallization in a total time of 20 to 120 minutes or more, including water vapor.
or the solid crystalline phosphoric acid catalyst according to 2. 4. The solid crystalline phosphoric acid catalyst according to any one of claims 1 to 4, wherein the silicate raw material of the solid phosphoric acid catalyst is diatomaceous earth and synthetic porous silica. 5. The solid crystalline phosphoric acid catalyst according to any one of claims 1 to 4, wherein the phosphorus oxide is polyphosphoric acid. 6. A method for converting hydrocarbons, comprising contacting a hydrocarbon feedstock with a solid crystalline phosphoric acid catalyst as defined in any one of claims 1 to 5. 7. The process of claim 6, wherein the process for converting hydrocarbons is alkylation of aromatic hydrocarbons with an olefinic activator. 8. Temperature of 100° to 390°C for aliphatic hydrocarbons, 1
Pressure from 130 atm and 0.5 to 50 hr^-^1
8. A process according to claim 7, characterized in that it is an aromatic hydrocarbon alkylation process at hydrocarbon conversion conditions comprising a flow rate of . 9. Process according to claim 6, characterized in that the hydrocarbon conversion is a catalytic condensation process. 10. Catalytic condensation method at a temperature of 170° to 290°C and 6.
．． 10. A process according to claim 9, characterized in that the conversion conditions include a pressure of 8 to 102 atmospheres.