JP797H - Shape selective conversion method - Google Patents

Description

Detailed Description of the Invention The present invention provides a novel method in the presence of crystalline zeolitic material.
Regarding the dewaxing method. More specifically, the present invention relates to a linear paraffin.
And slightly branched paraffins and hydrocarbon supplies
From mixtures with other ingredients commonly found in raw materials
Hydrocarbon supply by selective conversion of paraffin
It relates to a method of removing said paraffins from a source material. Crystalline zeolites and especially aluminosilicate catalysts
The hydrocarbon conversion process used is described in patent specifications and scientific text.
As can be seen from both the contributions, it has been the subject of extensive research in recent years.
ing. Crystalline aluminosilicate is an extremely diverse charcoal
It was found to be particularly effective for the hydrofluoride conversion method,
National Patent Nos. 3,140,249, 3,140,252
3,140,251, 3,140,253 and
Described in many patents, including 3,271,418,
One is claimed. General in hydrocarbon conversion operations
Aside from its use as a catalytic catalyst,
Between one type of molecule that has the property of Louis and another type
It is possible to preferentially convert the one molecular species from the mixture.
It is also known that it can be done. In this type of operation, zeolitic molecular sieves,
That is, it has catalytic activity in its internal pore structure and is supplied
Certain ingredients of the raw material can enter within its internal pore structure,
You can invert this and other components (this is its shape
To enter the pores of the zeolitic material for
Zeolite having pores that substantially eliminate
Sexual molecular sieves are used. Shape-selective catalytic conversion is also
Known in the art, US Pat. No. 3,140,3
22, No. 3,379,640, and 3,395.
Claimed in 094. Various zeolitic materials and especially crystalline aluminosiri
Quates have been used in various catalytic conversion operations to date.
However, these prior art operations generally involve one or
It falls into two major categories. One type of roll
In the liquefaction operation, most of the components normally found in the charging raw materials are
Zeo with a large pore size large enough to receive the part
Lights were used. That is, these substances are large
They are called molecular sieves with a pore size, they are 6 to 13 ounces.
It is commonly stated that it has a pore size of strom
And is represented by zeolites X, Y and L. Also
Mordenite also falls into this category. Aluminosilicate
Other types have pore sizes on the order of 5 Angstroms.
Then, it selectively acts on normal paraffin and other molecular species
Used to substantially eliminate That is, the present invention
It can only be used for hydrocarbon processing in an extremely simple way.
Two types of aluminosilicates, normal paraffins
That only accept the ins and the hydrocarbon feedstock
There was something that accepted all the ingredients that are always present.
I didn't get it. A class of zeolitic molecular sieves
Slight branching without normal paraffins in the pore structure
You can even go in and out of the paraffin that has left
Has the ability to eliminate frequently branched isoparaffins
It has a unique screening property in terms of
By using b.
I found that I can do it. Thus normal para
Not only selective for fins, but also slightly branched
Raffins, and especially monomethyl-substituted paraffins
It is now also possible to carry out a selective hydrocarbon conversion operation for
It is possible. A zeolitic material exhibiting these properties is a normal paraffin.
Dewaxing, which was previously desired only to selectively remove inns
Product of increased economic value when used in operations
Found to have many increased and unexpected benefits in terms of
It was As previously mentioned, the crystallinity conventionally used in the prior art
Aluminosilicates fall into one of the two types above.
It That is, they are about 5 angstrom units of pores.
Of about 6 to about 15 angstroms
It has the size of the hole in the unit of m. 5 ounce straws
Aluminosilicates in units of units are normally aliphatic
Mixtures of compounds with isoaliphatic compounds and cyclic compounds
To selectively convert normal aliphatic compounds from
Is said to be shape selective. Second type aluminium
Replicates or 6 to 15 angstrom units
Aluminosilicates with pore size are generally unselected
It is said to be sex. That is, normally in the hydrocarbon feed stream
Virtually all molecules have the internal pore structure of this zeolite
You can go in and be converted. Thus good
A convenient way to confirm that it is a shape-selective catalyst
The catalyst is normal hexane and 2-methyl pen
Shown to selectively crack from a mixture with tongue
The inner pore structure of the catalyst is the former.
But the latter isocompound is
Because it cannot be done. The novel dewaxing method of the present invention is based on two types of conventional
Is commonly said to be in the middle of an aluminosilicate
Based on the use of zeolitic materials. I.e.
The catalyst of Ming is ZSM-5 type zeolite and its internal pores
Normal aliphatic compounds and slightly branched in the structure
May contain aliphatic compounds, especially monomethyl-substituted compounds
Yes, but containing at least quaternary carbon atoms
All compounds equal to or equal to the quaternary carbon atom
Virtually all compounds with larger molecular dimensions
This is eliminated. Normal fat mentioned above
Similar to family compounds and slightly branched aliphatic compounds
The aromatic compound having a side chain has an internal pore structure of the catalyst of the present invention.
The side chain can be inserted in. Therefore if
Used in the present invention by the prior art tests described in
Selectivity of zeolitic materials, that is, hexane and isohexane
Selectively cracking hexane from a mixture with xane
If we had to measure our ability to
It must be stated that the medium is non-selective. Shi
Scarecrow selectivity is normal paraffin and isoparaffin
Much greater than the mere ability to selectively distinguish between
It is immediately clear that it has significance. About shape
The selectivity of is theoretically for any shape or size
Is also possible. But, quite clearly,
Such selectivity can be applied to any and all hydrocarbon conversion operations.
It is not an advantageous catalyst for production. The novel dewaxing process of the present invention produces aromas in most of the refining operations.
Desirable to preserve the tribe and remove normal paraffins
It is the recognition of the trader that it is bad, but
This general theory is the maximum of products of increased economic value.
Based on the fact that it is not the final word in obtaining the yield of
It is a waste. Now simply select normal paraffin
Not only to convert into some but also some isoparaffins
Can, but hope in a given feedstock
Increased by designing a catalyst system that does not act on bad components
They found that they could make a profit. This type of molecule
The process or sieve was previously unknown. I already said
Conventional contact involving the use of zeolitic molecular sieves.
The process only gave the driver two choices.
It was. He is a catalyst of non-selective capacity, i.e. charcoal water
Acts on virtually all molecules commonly found in elementary feedstocks
Using a molecular sieve that is a catalyst for
About 5 angstroms that selectively converts only aliphatic compounds
It is possible to use a catalyst with a pore size in the unit of memes.
It was either possible. Want to be bound by any theory of manipulation
Crystalline zeolitic material used in the present invention
Quality refers to the size of a hole or a range of hole sizes.
It seems that it cannot be simply characterized. this
The uniform pores of the new type of zeolites are
Of circular nature, like the usual case in lights
Rather, rather seems to be of elliptical nature
Be done. Therefore, the pores of the zeolitic material of the present invention have long and short axes.
A new molecular sieve that has both axes and is unusual
It is for this reason that the use can be achieved. This ellipse
The circular shape can be referred to as a "keyhole". This
The zeolite of the present invention is
The effective size displayed by the size of a large molecule is elliptical.
The short axis is about 5.5 angstrom units and the long axis is 6
I think it is in one of the 9 angstrom units.
Be seen. The unique pore-molecule sieving action of these substances is
These elliptical shapes that control the entry and exit of the internal crystal into and from the pore structure
It is probably based on the existence of shaped windows. Hydrogen type ZSM-
5 or HZSM-5 hole inlet effective dimensions are
Diffusion rate by measuring half-absorption time for elementary molecules
It can be measured from the degree. n-hexane and 2-methyl pen
Prompt adsorption at low temperature such as 93 ℃ for tan
Can be Both are semi-sorption time (t_0.5)
However, at higher temperatures, sorption is too fast
I could not measure. Cyclohexane takes about 42 seconds at 93 ° C
Of t_0.5It shows that the sorption is too fast at 150 ° C or higher.
I can't come. In contrast, 2,2-dimethylbutane has several orders of magnitude
Adsorbed slowly and 9 for 2,2-dimethylbutane
T at 3 ° C_0.5Takes 1940 seconds, even at 204 ° C_0.5
Was 21 seconds. For example, Court Olds (Coutauld
s) As you can see from the model, cyclohexane and 2,2-
Investigating the molecular model with dimethylbutane, their criticality
The dimensions are similar and both are about 6 angstroms
However, their cross-sections have different shapes (ie cyclohex
Sun is 6 × 4.7Å and 2,2-dimethylbutane is 6 ×
5.6 Å). The cross section of cyclohexane is roughly elliptical
2,2-dimethyl having a quaternary carbon atom
In Butane it is round. The expansion between these two molecules
A significant difference in the rate of dispersion is the ZSM-5 type "keyhole"
Reflects the difference in the ability of those molecules to enter the entrance hole
However, these and other sorption data are 6-9 on the long axis
Gstrom and the short axis is about 5.5 Å
Suggests that it has an elliptical window (hole) with
It These elliptical inlet holes are used in other ZSM-5 series
This is a common feature of Olite. In other words, the zeolites of the present invention are subject to conversion conditions or dewaxing.
Normal aliphatic compounds and slight branching under reaction conditions
Included aliphatic compounds, especially monomethyl-substituted compounds
But compounds containing quaternary carbon atoms can enter
It cannot be an effective dimension, that is, an elliptical shape whose long axis is 6Å or
9Å, the minor axis has a hole with an effective size of about 5Å. The unique properties required to carry out the novel conversion operations of the present invention
ZSM-5 type zeolite which is a molecular zeolite
The determination of olite is mainly based on its chemical composition and X-ray diffraction pattern.
The following test method
To easily confirm that the
You can also In the test method, the matrix or binder
The test zeolite without a
Change into a prototype. This operation is a metal cation that originally exists
Replacement with ammonium chloride solution.
Nau. Next, make a sample with a size of 20 to 30 mesh,
Bake in air at 550 ° C. for 16 hours. Processed like this
1 g of the prepared zeolite is then added at 12 ° C. for 2 hours at 25 ° C.
Contact with benzene under pressure. Other 1g sample at 25 ℃
Contact with mesitylene at a pressure of 0.5 torr for 6 hours
It Zeolites that can be used are those whose acid form is
Adsorb at least 3.0% by weight of Zen and remove mesitylene
It adsorbs less than 1.5% by weight. Zeolite materials that can be used in the method of the present invention are ZSM-5 type.
Of zeolite. ZSM-5 type material is patent No. 61
No. 9824 (Japanese Patent Publication No. 46-10064)
There is. ZSM-5 type zeolite has the characteristics described in Table 1 below.
X-ray diffraction diagram. The ZSM-5 composition is an oxide model.
It can be identified as follows in the form of a ratio.In the formula, M is a cation containing hydrogen and is a valence of the cation.
Z is a value of 0 to 40. In a preferred synthetic form, the zeolite is a mole of oxide.
It is expressed as follows in the form of a ratio. However, M is an alkali metal cation, especially sodium and
Group consisting of mixtures of traalkylammonium cations
Chosen from. The tetraalkylammonium cation
Preferred alkyl groups containing 2 to 5 carbon atoms
And In a preferred embodiment of ZSM-5, silica / alloy
The molar ratio of mina ranges from at least 10 up to about 60.
It The synthetic zeolite is calcined into a catalytic form. that time
If necessary, ion exchange may be carried out so that at least part of M is
turn on. M in the synthetic type is tetraalkylammo
It is converted to hydrogen ions during firing like the cations of
If no ion exchange is required, These steps are Zeo
This is a well-known process when using Wright as a catalyst, and will be described later.
It is also shown in the examples. The X-ray diffraction pattern of ZSM-5 zeolite type zeolite is as follows.
Has a distinctive crystalline structure showing the major lines of.These values as well as all other data are according to standard techniques.
Was measured. The irradiation line uses a copper K-α twin line,
Scintillation counting with trip chart recorder
A tube spectrometer was used. Peak heights I and 2θ (here
Where θ is the Plating angle) and its position as a function of
It can be read from the chart of the spectrometer. From these
Relative intensity 100I / I_O(However, I_OIs a function of 2θ
Is the intensity at the position of, and θ is the platter angle)
You can read it from the spectrometer chart. From these phases
Against strength 100I / I_O(However, 1_OIs the strongest line or peak
Is the intensity of the line, and d (actual measurement) is the value corresponding to the recorded line.
Calculate the lattice spacing expressed in ngström)
can do. In Table 1, the relative intensity is S = strong
Yes, M = medium, MS = relatively strong, MW = relatively weak
And VS = extremely strong. This X-ray diffraction diagram
Is unique to all types of ZSM-5 compositions
You should understand. Sodium ions and other cations
Even if it is replaced by
Was found to give virtually the same figure with slight variations
It was Depending on the silicon-to-aluminum ratio of a particular sample
And whether it has been subjected to heat treatment
Other subtle changes can occur. Various cation exchange
A modified version of ZSM-5 was produced. Of these several types
The X-ray powder diffractogram is given below. The following ZSM-5 type
Are all aluminosilicates. Table 2 Zeolite ZSM-5 is tetrapropylammonium hydroxide
Um, sodium oxide, aluminum, silicon and water
Table 3 below, in the form of a solution containing
A solution having a composition within the range of Table 3(R in the above table is a propyl group) Keep this mixture until zeolite crystals form
Can be manufactured by. Then the crystals from the liquid
Separate and collect. Typical reaction conditions are the above reaction mixture
To about 150 ° C to 175 ° C for about 6 hours to 60 days
Consists of heating over. More suitable temperature range
About 160 ° C to 175 ° C.
The period in degrees is about 12 hours to 8 days. Digestion of the obtained gel particles is continued until crystals are formed.
By cooling the whole to room temperature and filtering the solid product.
Separated from the reaction medium and washed with water. For example, the above product at 110 ° C (230 ° F) for about 8 hours
Dry for 24 hours. More mild conditions, if desired
It goes without saying that room temperature can be used under reduced pressure, for example.
Yes. ZSM-5 is produced as an aluminosilicate. This
Compositions are made using materials that supply the appropriate oxides
be able to. Such compositions are aluminosilicates
In case of formation sodium aluminate, alumina, silica
Sodium acid, silica hydrosol, silica gel, silica
Acid, sodium hydroxide and tetrabropiru hydroxide
Contains monium. Build a ZSM-5 series
Each of the oxide components used in the reaction mixture for
Supplied as one or more initial reactants,
Can be mixed with each other in any order. For example acid
Sodium hydroxide with an aqueous solution of sodium hydroxide or
Can be supplied by aqueous solution of sodium silicate
It Tetrapropylammonium cation bromides this
It can be supplied by salt. ZSM-5 crystals
The size and crystallization time depend on the nature of the reaction mixture used.
Therefore, it changes. The zeolite used in the present invention may be prepared by any technique known to those skilled in the art.
To zeolites that are replaced by various other cations
Primitively bound cations can be replaced. Generation
Surface substitution cations are hydrogen, ammonium and metals
Includes cations and mixtures thereof. Substituted metal io
Especially preferred are rare earth metals, manganese, and calcium.
Group II metals in the periodic table, such as zinc, and the periodic table
It is a Group VIII metal such as nickel. A typical ion exchange technique is the desired substitution cation or
To bring the on-salt into contact with the specific zeolite
It Various salts can be used, especially chlorides,
Nitrate and sulphate are preferred. A typical ion exchange technique is U.S. Pat. No. 3,140,24.
No. 9, 3,140,251 and 3,140,253
It is disclosed in various patents including the specification. Zeora after contacting with a solution of the salt of the desired substituted cation
Wash the iron with water, preferably at 65 ° C (150 ° F) to about
Dry at temperatures in the range of 316 ° C (600 ° F), then
260 ° C (500 ° F) in air or other inert gas
To 816 ° C (1500 ° F) for 1 hour
Sinter for 48 hours or longer. According to the invention
With improved selectivity, like contact cracking
A catalyst with other advantageous properties for certain hydrocarbon conversion operations.
The medium is zeolite 426 ° C (800 ° F) to 816 ° C
(1500 ° F) and preferably 537 ° C (1000 ° F)
At elevated temperatures ranging from 760 ° C (1400 ° F)
It is further determined that it can be obtained by treating with steam.
Revealed This treatment is performed in an atmosphere of 100% steam or water.
Consists of gases substantially inert to steam and zeolites
It is done in an atmosphere. Similar treatments include lower temperatures and elevated pressures such as 176 ° C.
10 atm to about 2 at -371 ° C (350-700 ° F)
It can be achieved at 00 atm. Zeolite is tongue
Stainless, vanadium, molybdenum, rhenium, nickel
Ru, cobalt, chromium, manganese or platinum or palladium
Tight coupling with hydrogenated components such as precious metals like um
Can also be used in this case, in which case hydrogenation /
Dehydrogenation function, ie shape-selective hydrocrackin
Such an ingredient capable of effecting i
Exchange, impregnate into the composition, or physically intimately mix
can do. In the case of platinum
By treating the zeolite with ions containing platinum.
Can be impregnated in or on the zeolite.
It Thus, suitable platinum compounds include chloroplatinic acid, salts
Various compounds containing platinum chloride and platinum ammine complex
The compound is included. Compounds of platinum or other useful metal compounds are
A compound having a genus in the cation part of the compound, and the metal
Is classified as a compound existing in the anion part of the compound.
You can Forming of both types containing metal in ionic state
Compounds can be used. Platinum metal is a cation
Is a cation complex form such as Pt (NH_Three)_FourCl_TwoExist
Existing solutions are particularly useful. Zeolites should be at least partially dehydrated before use
is there. This is for example empty at temperatures in the range of 200-600 ° C.
To atmospheric pressure in an inert atmosphere such as air or nitrogen.
Or heated under atmospheric pressure for 1 to 48 hours
Can be done by doing. Dehydration also requires decompression
Just to use but to get enough dehydration more
It takes a long time but can be achieved at a lower temperature
It As mentioned above, the novel process of the present invention is a hydrocarbon source.
Regarding dewaxing of charges. In the specification and claims
The dewaxing used is used in its broadest sense.
To remove (wax) hydrocarbons that easily solidify from
To taste. It can be further processed as described in the specific example.
The hydrocarbon feedstock that can be produced has a freezing point or flow similar to that of lubricating oil.
Raw material with a fixed point problem, ie about 176 ° C (350 ° F)
Petroleum raw materials that boil above are included. Dewaxing is black
Can be performed under hydro- or hydrocracking conditions
it can. Typical cracking conditions are about 0.5 to 200
Liquid hourly space velocity, about 287 ° C (550 ° F) to 59
3 ° C (1100 ° F), no pressure below atmospheric pressure
This includes pressures of several hundred atmospheres. When performing hydrocracking operation, the operating conditions are
343 ° C (650 ° F) to 538 ° C (1000 ° F)
Temperature, pressure of 100 psig to 3000 psig but preferred
Or pressure of 200 psig to 700 psig. liquid
The body-temporal space velocity is generally 0.1 to 10, preferably
0.5 to 4 and the hydrogen to hydrocarbon molar ratio is generally
It is 1 to 20, preferably 4 to 12. The following examples are the best modes contemplated for carrying out the invention.
To explain. Example 1 This example is a typical production method of zeolite ZSM-5, 2.18 standard.
About 1 in 100 ml of constant tetrapropylammonium hydroxide
Partially melted by heating to 00 ° C. next
H_TwoDissolved in 53.8 ml O. NaAlO_Two3.19
g (composition Al_TwoO_Three42.0% by weight, Na_TwoO30.9
%, H_TwoO2 7.1%) is added. The resulting mixture
The compound had the following composition. SiO_Two0.382 mol, Al_TwoO_Three0.0131 mo
Le, Na_TwoO 0.0159 mol, [(CH_ThreeCH_TwoCH
_Two)_FourN]_TwoO 0.118 mol, H_TwoO 6.30 mol.
Pyrex lined autoclave with this mixture
And heated at 150 ° C. for 6 days. Obtained solid formation
The product was cooled to room temperature, the solid was separated, filtered and washed with water 1
Washed at 110 ° C. (230 ° F.) and dried. This generation
Part of the product was subjected to X-ray analysis and confirmed to be ZSM-5.
I knew it. A part of the product is heated to 538 ° C (1000 ° C) in air.
After baking for 16 hours in F), the following analytical values were obtained. analysis
As is clear from the value, the cation is 50 mol of hydrogen ion.
%, 50 mol% sodium ion. Table 4Example 2 ZSM-5 made as described in Example 1 confirmed
Zeolite samples in air at 534 ° C (1000 ° F)
Calcined for 16 hours, and then the ability to decompose Amar gas oil
evaluated. Amar gas oil used is C-18 to C
Contains 25.2% by weight of normal paraffin in the range of -38.
Boiling point of 343 ° C to 454 ° C (650 ° F to 850 ° F)
It was a waxy amargas oil in the point range. This Amar gas oil is ZSM-5 and 107WHSV,
Contact at 0.56 catalyst / oil ratio and 482 ° C (900 ° F)
Let Amar gas oil containing waxy normal paraffin
The amount was reduced from 25.2% to 4.1% by weight.
It is shown in the analysis value. Comparative example Salt with commercially available zeolites or lanthanum salts
Group-exchanged zeolite A was used instead of ZSM-5
The procedure of Example 2 was repeated except otherwise. More troublesome than the operation of Example 2.
Severe operating conditions, that is, reducing space velocity to 6 WHSV,
Normal paraffins even with increasing catalyst / oil ratio to 1
Although the content could be reduced to 16.5% by weight,
I didn't get it. That is, comparison of the results between Example 2 and Comparative Example
Higher molecular weight waxy norms than previously impossible
Shows that ruparaffin can be significantly reduced
This is the form in which these long chain molecules were previously available.
It tends to block the pores of selective molecular sieves, which
Cause problems with diffusivity, which leads to unfavorable results.
This is due to the fact that Example 3 In this example, the catalyst used in the method of the present invention is normal paraffin.
Can not only be converted into
It also converts harmful, slightly branched paraffins
Due to the fact that the hydrocarbon feed treatment of the present invention
It is intended to explain the improved results obtained. The same waxy amargas oil used in Example 2 was
Subjected to conventional extraction techniques using olite. Amar
Practically all normal paraffins are removed from gas oil
This extraction was continued until. This is not a catalytic reaction type treatment
It is simply a conventional extraction process. This Amar gas oil
Has a pour point of 37.8 ° C (100 ° F) and
Pour point is 4.4 ° C (40 ° F) after removing all fins
Fell to. A ZSM-5 catalyst prepared as described in Example 1 was used.
Shape another part of the same waxy amar gas oil using
It was subjected to a dynamic conversion treatment. This treatment is 482 ° C (900 ° F)
Space velocity of 107 WHSV and 0.56 for 10 minutes at
Performed at catalyst / oil ratio. By this treatment, -20.6 ° C (-
The 650 ° F + fraction with a pour point of 5 ° F) was recovered.
3.6% by weight of normal paraffin remained. That is, the pour point drop is due to the removal of normal paraffins.
But that's the complete answer for pour point depreciation
You can know that not. Novel method of the invention
Is the pour point even if all normal paraffins are not removed.
Causes a significant descent. Any theory about this process
I don't want to be bundled by
Regular catalysts are slightly branched, which has a detrimental effect on the pour point.
It seems that the paraffin will also be converted. Example 4 ZSM-5 zeolite according to the general technique described in Example 1.
Made. Then it was originally bound to the zeolite
Solution of ammonium chloride to exchange cations
Contact with liquid, then wash with water, dry and dry in air
Hydrogen type or H- by firing at 538 ° C (1000 ° F)
Changed to ZSM-5. Elionite (pore of about 3.6 x 5.2 angstrom)
Natural crystalline aluminosyrike identified as
Similar treatment with ammonium salt, and then
These two substances were added to normal hexane and 2,3-di
Normal hex from a mixture of methylbutane and benzene
Sun 15: 1H_Two/ Hydrocarbon ratio, pressure of 200 psi
And its ability to selectively decompose at 371 ° C (700 ° F)
I evaluated it. Operate these materials for 15 minutes and 3
Evaluated with respect to time. The results obtained are as follows
there were. The above table is a truly excellent surprise obtained using the catalyst of the present invention.
It clearly and prominently explains the deplorable result. Sanawa
After 15 minutes of operation, hydrogen-type erionite and H-
The conversion with ZSM-5 is virtually the same. This is
Both of these substances are extremely active cracking catalysts.
So it's not surprising. But after 3 hours
The data obtained in general
It loses activity but does not degrade the H-ZSM-5 catalyst. sand
It was totally unexpected that activity would not be lost.
is there. As you can see from the table above, the conversion rate with erionite is
It fell to 33.7%, which clearly indicates deterioration.
-Conversion rate with ZSM-5 remains virtually unchanged after 3 hours.
This explains that the catalyst did not deteriorate.
It is something. Example 5 Shape Selectivity and Prior Art Obtained Using the Catalyst of the Invention
Example 2 to illustrate the difference in type from the shape-selective substances of
The same waxy amar gas oil used in
A (ie Linde 5A, which is the NATO in zeolite A)
By replacing the cation of calcium with calcium
And has a pore diameter of about 5 Å).
Crystalline aluminosilicate and ZSM-5 identified by
Comparison of shape-selective cracking with fired samples
went. Below is a comparison of the products obtained by decomposing the same raw materials.
Shown in the table.The coke yield obtained by the novel method of the present invention is
Coke yield obtained using a classical shape-selective material of technology
It is apparent that it is significantly lower than further
Gasoline production or C₅-C₁₂Is calcium-A type
It is considerably higher than that of the catalyst. Further according to prior art
Classic shape-selective catalysts are always C_FourRich in hydrocarbons, and vice versa
C₅-C₁₂This produces a low hydrocarbon product. From the table above
As you can see, this is the case when using a ZSM-5 type catalyst.
No nagging, not just normal paraffin
Showing that the paraffins branched into are also converted
There is. The improved results mentioned above are illustrated by the table above.
Believe that The following example is water combined with ZSM-5 type catalyst.
Improved results with the use of elementary addition / dehydrogenation components
It is possible to Example 6 A ZSM-5 type catalyst was prepared according to the general procedure of Example 1.
It was The characteristics of the reaction composition and final product are as follows:
is there.The above materials are then placed at about 538 ° C (1000 ° F) for 16 hours.
Baking, which was divided into two parts. Part A
1 hour at room temperature, 0.05 normal solution of ammonium chloride 100
Replaced with ml to ammonium salt. This is catalyst A1
I named it. 4g of catalyst A1, 3g at 43 ° C (109 ° F)
2.9 / 1 zinc / NH with 0.5 time_FourChloride solution 3
Replaced with 5 ml. This material is then washed with water and dried in air.
Dried and zinc content 0.9% by weight and sodium content 0.2
A catalyst was obtained having a weight percentage of. Name this catalyst A2
It was Treat Part B with anhydrous ammonia (100 cc / min) at room temperature
Then NH_FourRebuilt the territory. Name this catalyst B1
I got it. 3 g of catalyst B1 were mixed with zinc chloride and salt solution as described above.
It was exchanged with a 0.5 N solution of monium. The final catalyst is
It contains 1.2% by weight of zinc and 0.3% by weight of sodium.
This was named B2. Example 7 The catalyst B2 described above is treated by hydroprocessing technology.
The pour point depression of ale oil was evaluated. Raw material
Is a full range dehydration with a pour point of about + 26.7 ° C (+ 80 ° F)
It was sheer oil. Typical composition during the distillation
Is shown in the table below.500 psig of the above Sierle oil, 4LHSV42
Hydrogen at 7 ° C (800 ° F) and 2000SCS / BBL
The catalyst B2 was brought into contact with the circulating amount. The result obtained is the pour point
It has a temperature of −26.1 ° C. (−15 ° F.). 97% by weight recovery
The amount is shown. Has a pour point of -26.1 ° C (-15 ° F)
The analysis of the liquid product showed that olefin was saturated and
The transition to low boiling point products is shown, as shown in the table below.
Increasing the content of fusa and light fuel oil, in contrast to C_{twenty two}Yo
The larger range of products (higher products) is decreasing.Example 8 This example shows the production of lubricating oil by the shape-selective hydrodewaxing method.
To explain. The lubricating oil charging raw material used had the following properties. Specific gravity Å PI 31.9 Pour point ° F +85 (29.4 ° C) Sulfur weight% 0.17 Hydrogen weight% 13.23 Kinematic viscosity (KV) 100 ° F (37.7 ° C), cs 19.27 Kinematic viscosity (KV) 210 ° F (100 ° C.), cs 3.93 Viscosity index 108.4 Vacuum distillation test ° F Initial boiling point 669     5% 696   10% 707   30% 737   50% 766   70% 795   90% 834   95% 847 The above charge was made as described in Example 6, B2.
Hydrodewaxing Treatment Using Different Zinc / H-ZSM-5 Catalyst
Attached to. The experimental results and operating conditions obtained are shown in the table below.
Shown in.From the above table, the catalyst of the present invention has a pour point from the original value of 85 ° F.
Can you see that it has been significantly lowered to a low value such as 40 ° F?
It The above results show that the novel catalytic treatment of the present invention has increased value.
It is desirable to hydrodewax the feed to obtain a good product
It suggests that it can be used in new places.
One such location is an automatic transmission fluid. Up
The method is an alternative to the conventional solvent dewaxing process currently used.
Can be used instead. The other way is specific
The pour point is obtained by subjecting the raw material to a conventional solvent dewaxing process.
Lower to the intermediate stage, after which the product is shape-selectively deoxidized.
(C) It is possible to lower the pour point by applying treatment.
Recognize. As can be seen from the above, the novel processing method of the present invention is
Greater flexibility in refining the production of commercially important products
It is to be given. Example 9 This example illustrates shape-selective hydrodewaxing of lubricating oil feedstocks,
To be able to achieve hydrocracking of long-chain molecules again
Will be explained. The charging raw material used is Mitsudo Conti with the following specifications.
It was the top fraction of the Nent vacuum distillation column. Specific gravity Å PI 32.2 Specific gravity 0.8644 Vacuum distillation test ° F Initial boiling point 550   5% 596 10% 630 30% 646 50% 662 70% 684 90% 728 95% 756 Pour point ° F (D-9 +50 Flash point Point) ゜ F 345 Viscosity SUS100 ° F (37.8 ° C) 57.7 Viscosity SUS130 ° F (54.4 ° C) 45.8 Viscosity SUS210 ° F (100 ° C) 34.5 Kinematic viscosity 100 ° F (378 ° C) 10.56       210 ° F (100 ° C) 2.50 Viscosity index 56 Aniline NO. ° F 182.2 This charge was made according to the technique described in Example 6 (B2).
The catalyst was contacted with Zn / H-ZSM-5. operation
The conditions are generally mild hydrocracking conditions, ie
500 psi, 371 ° C (700 ° F), 4 LHSV and
And the hydrogen to hydrocarbon molar ratio was 30. The results obtained
It is shown in the table below. Operation time (hours) 2 Conversion rate% by weight 33.5 Yield weight%   C₁+ C_Two            1.4   C_Three                      5.4   C_Four                    10.1   C₅+2 decomposition product 16.6   Unconverted compound 66.6   Pour point of unconverted material F-85 ° As can be seen from the above data, the novel method of the present invention is
Decrease the pour point of the product considerably. That is, from + 50 ° F to -8
A drop of 5 ° F or 4.5 ° F per 1% conversion. yield
7 for liquid products above 316 ° C (600 ° F)
It was 0% by weight. This example is based on the novel detreatment technology of the present invention.
The improved results that can be obtained
It Example 10 This example shows a low freezing point and high BTU diet manufactured by the novel method of the present invention.
It describes the production of fuel. 177-260 ° C (350-500 ° F) Amaruna
Amal-Nafoora kerosene has the following properties
Have. Specific gravity Å PI 48.1 Freezing point ° F -27 Aromatic (FIA) volume 9.1 Aniline No. ° F 156.9 Calorific value BTU / 1b 18710 This charge was made by the technique described in Example 6 (B2).
Contacted with Zn-H-ZSM-5 catalyst. Operating condition is 5
00 psig, 343 ° C (650 ° F), 24 LHSV,
H_Two/ Hydrocarbon molar ratio was 15: 1. For the above operation
A dewaxed product yield of 78.5% was obtained,
Are shown in the table below together with the properties of JP-7 jet fuel. The results shown in the above table indicate that the novel method of the present invention is Amar kerosene.
Explain the fact that it can significantly lower the freezing point of
It is something. However, the calorific value and aromatic content of the product
Note that the specifications for JP-7 jet fuel are not met
You should see it. Hydrogen to increase heating value and reduce aromatic content
The dewaxed product can be subjected to mild hydrogenation.
Wear. In this regard, 20 g of hydrodewaxed product, sikh
100 ml of rohexane, reduced nickel or diatomaceous earth (H
3 commercial catalysts including ArshawNi0107)
Charge to a 00ml stirring autoclave, 500ps
A hydrogen pressure of ig was applied. Mix the above mixture for about 2 hours 30
Heat at 8 ° C-316 ° C (587-600 ° F) during this period
Final pressure between about 1200-1300 psg
It was. Recovery of 93% by weight of hydrogenated product by the above operation
The hydrogenated product had the following properties: Specific gravity Å PI 47.5 Freezing point ° F (° C) -81 (-62.8) Aromatic (FIA) volume% 4.0 Aniline No. ° F 179.0 Calorific value BTU / 1b 18835 From the above table, the novel method of the present invention has a low freezing point and a high BTU content.
To provide a method for producing a jet fuel having a quantity
I understand.

Claims (1)

1. A mixture of straight-chain hydrocarbons and slightly branched hydrocarbons with other compounds having different molecular shapes, having a generally elliptical shape. Under conversion conditions, the elliptical major axis has pores with an effective dimension of 6Å to 9Å minor axis of about 5Å, the straight chain hydrocarbons and slightly branched hydrocarbons having in their internal pore structure A crystalline zeolitic material which can enter and be converted, having the general formula 0.9 ± 0.2 M ₂ / nO: Al ₂ O ₃ : 5-100SiO ₂ : expressed in the form of the molar ratio of the oxides. ZH ₂ O (wherein M is a cation including a hydrogen ion, n is a valence of the cation, and z is a value of 0 to 40) and has a main line shown below. Linear hydrocarbons and slightly branched from the mixture upon contact with a crystalline zeolitic material having a line diffraction pattern Dewaxing method characterized by selectively cracking the hydrocarbons. Lattice plane spacing d (A) 11.1 ± 0.2 10.0 ± 0.2 7.4 ± 0.15 7.1 ± 0.15 6.3 ± 0.15 6.04 ± 0.1 5.97 ± 0.1 5.56 ± 0.1 5.01 ± 0.1 4.60 ± 0.08 4.25 ± 0.08 3.85 ± 0.07 3.71 ± 0.05 3.64 ± 0.05 3.04 ± 0.03 2.99 ± 0.02 2.94 ± 0.02