CN1090159C - Process for selective hydroisomerisation of long linear and/or slightly branched paraffins using catalyst based on molecular sieve - Google Patents
Process for selective hydroisomerisation of long linear and/or slightly branched paraffins using catalyst based on molecular sieve Download PDFInfo
- Publication number
- CN1090159C CN1090159C CN96121074A CN96121074A CN1090159C CN 1090159 C CN1090159 C CN 1090159C CN 96121074 A CN96121074 A CN 96121074A CN 96121074 A CN96121074 A CN 96121074A CN 1090159 C CN1090159 C CN 1090159C
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- compound
- charging
- weight
- desire
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
- C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a selective hydrogenation isomerization method of a compound, which comprises at least one straight chain alkyl chain containing more than 10 carbon atoms, wherein a compound to be treated is in contact with a catalyst; the catalyst comprises at least one hydrogenation-dehydrogenation element and at least one molecular sieve having a one-dimensional or two-dimensional hole net, wherein the opening of an accessible hole is limited to 10 oxygen atoms; the distance among holes which are defined as the width of a bridge is smaller than 0.70 nm; moreover, when an isomerization experiment of a standard n-Heptadecane is carried out, the selectivity of the catalyst is at least 70%, and the conversion rate of an isomerization product is 95%.
Description
The present invention relates to (surpassing 10 carbon atoms) straight chain of a kind of length and/or the selective hydrogenation isomerization method of slight ramose paraffinic hydrocarbons, particularly relate to a kind of charging high productivity and transform at least a method with cut of low pour point and high viscosity index (HVI) with high pour point.
High-quality lubricating oil has very important significance for effective running of modern mechanical, car and truck.But, to compare with the demand that lubricating oil is growing, the quantity that is directed to untreated crude oil and has a paraffinic hydrocarbons of high-quality lubricants performance but is low-down.
After must handling, the heavy oil fraction that contains a large amount of straight chains or slight ramose paraffinic hydrocarbons could obtain having the lubricating oil of better quality with high as far as possible yield.Adopt dewaxing process eliminating straight chain or very slight ramose paraffinic hydrocarbons from charging, the material after the processing can be used as lube stock or as kerosene or jet fuel.
The straight chain or the very slight ramose high molecular weight paraffinic that are present in oil, kerosene or the jet fuel have very high pour point, and this makes it can condense when low temperature.In order to reduce pour point, must remove these straight chains or very slight ramose paraffinic hydrocarbons wholly or in part.
Use such as propane or methylethylketone (MEK) extract to implement the dewaxing operation as solvent.But the distinct disadvantage of this technology is expense height, length consuming time, and this technology is always not easy to implement yet simultaneously.
The another kind of WITH CATALYTIC DEWAXING TECHNIQUE relative with solvent dewaxing process is then more economical, can produce the product with desirable physical-chemical property again simultaneously.Can realize above purpose by the linear paraffins chain that selective cracking process is the longest, form low-molecular-weight compound thus, a part wherein can be removed by distillation.
Because zeolite has the form selectivity, thereby they are the most widely used dewaxing catalysts.Adopting zeolite is the structure that comes from himself as dewaxing catalyst, because the hole opening in the zeolite can allow long-chain or very slight ramose paraffinic hydrocarbons to enter in its micropore, branched paraffin, naphthenic hydrocarbon and aromatic hydrocarbons then are left out.This situation causes and can carry out selective cracking process to straight chain or very slight ramose paraffinic hydrocarbons.
Zeolite based catalysts such as the known cracking process catalytic dewaxing process that can be used for of ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM35 and ZSM-38 with intermediate pore size.
Use the method for these zeolites to comprise less than the straight chain of 50 weight % or very slight ramose paraffinic feedstock and realize dewaxing by cracking.But when the content of these compounds in the charging was high, cracking process can cause forming a large amount of low-molecular-weight compounds, as butane, propane, ethane and methane, it is believed that, these materials can significantly reduce the yield of purpose product.
In order to address these problems, we have carried out deep research to the catalyzer (preferred non-ZMS) that can make these compound isomerizates.
In this research field; to the existing many patent documentation reports of the problems referred to above; describe and claimed a kind of method that charging is dewaxed by isomerization method as WO 92/01657; this method is in the presence of the group VIII metal; in hydrogen-pressure is under the condition of 100KPa-21000KPa; employing has the hole opening to be carried out for the 0.48nm-0.71nm catalyzer, and wherein grain-size is less than 0.5 μ m.Compare with the catalyzer of prior art, this catalyzer can improve performances such as yield.
The invention provides a kind of to comprising that at least one compound that contains 10 nalka hydrocarbon chains more than the carbon atom carries out the isomerized method of selective hydrogenation, the compound that desire is handled contacts with a kind of catalyzer, said catalyzer comprises at least a hydrogenation-dehydrogenation element and at least a molecular sieve with one dimension or two-dimentional hole pattern, wherein the opening in enterable hole is limited to 10 Sauerstoffatoms, distance definition between Kong Yukong is that bridge is wide, this value is less than 0.70nm, and, when the isomerization test of the n-heptadecane of carrying out standard, selectivity of catalyst is at least 70%, and the transformation efficiency of isomerized product is 95%.
Advantageously, present method can will have the feedstock conversion of high pour point become to have the mixture of low pour point and high viscosity index (HVI).
Charging also comprises and contains at least 10 carbon atoms, preferred 15-50 carbon atom, the advantageously straight chain of 15-40 carbon atom or/or very slightly the ramose alkane is light.
Present method comprises uses following catalyzer: this catalyzer comprises at least a molecular sieve, and said molecular sieve has at least a hole type, and its opening is determined by 10 Sauerstoffatoms, can said pass be maximum pass from the structure that the outside enters at it.The hole pattern of zeolite is one dimension or two dimension, preferred unidimensional hole pattern.
Bridge width (10 Sauerstoffatoms) between two hole openings is less than 0.70nm (1nm=10 as defined above
-9M), preferred 0.50nm-0.68nm, more preferably 0.52nm-0.65nm.Grain-size is preferably less than 2 μ m (1 μ m=10
-5M), be more preferably less than 1 μ m, preferably 0.4 μ m.
Below in the n-heptadecane isomerization test (SIT) of the standard that will describe, the feature of catalyzer of the present invention also is, the transformation efficiency of n-heptadecane (n-C17) is being about 95 weight %, is 70% or bigger to the selectivity of isomerized products, preferably is at least 80%.Product after the isomerization comprises the product of the multiple-limb of the single subsidiary product of about 65 weight %-80 weight % and 20 weight %-35 weight % usually, is two ramose products substantially.Term " single subsidiary product " is meant that straight-chain paraffin only comprises a methyl, and term " two subsidiary product " is meant the straight-chain paraffin that comprises 2 methyl that carried by different carbon atoms.The multiple-limb product also can broadly define.Therefore, hydrogenation isomerization has selectivity.
Catalyzer also comprises at least a hydrogenation-dehydrogenation functional group, for example group VIII metal and/or group vib metal and/or rhenium and/or niobium, and reaction is carried out under the following conditions.
Be surprisingly found out that one of determinative of isomerized product being obtained highly selective is to use the molecular sieve with following feature:
The opening in maximum hole is limited by 10 Sauerstoffatoms;
The bridge width must be less than 0.70nm, preferred 0.50nm-0.68nm, more preferably 0.52nm-0.65nm.
A difference last with above-mentioned prior art such as International Application No. WO 92/01657 claimed technology is that basic feature is the quality of the size decision isomerization product yield in hole in the prior art.
The bridge width is to use molecular model and drawing process to measure as Hyperchem or Biosym method, and they have constructed the surface of related molecular sieve, uses the ionic radius that is present in the element in the framework of molecular sieve to measure the bridge width.
Use molecular sieve of the present invention can produce product with high yield under these conditions with low pour point and high viscosity index (HVI).
It is zeolite, crystal aluminosilicate than the molecular sieve of straight chain or slight branched chain alkane that the present invention can be used for isomery, as Theta-1, NU-10, and NU-23, EU-13, wherein Si/Al ratio preferably should be suitable for desired purposes.Zeolite of the present invention is also selected the NU-87 zeolite for use, and it has definitely by 10-12 the hole that Sauerstoffatom limited, but can enter the latter by the hole opening with 10 Sauerstoffatoms.The present invention also comprises following zeolite: promptly aforesaid zeolite comprises the zeolite derivative of at least a heteroatoms such as B, Fe, Ga or Zn in its skeleton.
Used NU-10 zeolite and the synthetic method thereof of the inventive method described in EP-A-0 77 624.The feature of NU-10 zeolite is provided by following X-ray diffraction table:
The X-ray diffraction table of NU-10 zeolite
| d (A) | l/l o |
| 10.95±0.25 | m-S |
| 8.80±0.14 | w-m |
| 6.99±0.14 | w-m |
| 5.41±0.10 | w |
| 4.57±0.09 | w |
| 4.38±0.08 | VS |
| 3.69±0.07 | VS |
| 3.63±0.07 | VS |
| 3.48±0.06 | m-S |
| 3.36±0.06 | w |
| 3.31±0.05 | w |
| 2.78±0.05 | w |
| 2.53±0.04 | m |
| 2.44±0.04 | w |
| 2.37±0.03 | w |
| 1.88±0.02 | w |
Weak (the l/l of W=
oBe 0-20); Medium (the l/l of m=
oBe 20-40);
Strong (the l/l of S=
oBe 40-60); Very strong (the l/l of VS=
oBe 60-100).
The Si/Al atomic ratio of NU-zeolite is 8-1000.
Have found that, can in the catalytic test that is referred to as standard isomerization test (SIT), adopt pure heptadecane that catalyzer of the present invention is characterized.This test is carried out under the following conditions: the hydrogen dividing potential drop is 150kPa, and the dividing potential drop of n-heptadecane is 0.5KPa, and promptly total pressure is 150.5KPa, and test is carried out in fixed bed, and constant n-heptadecane flow velocity is 15.4ml/h, and catalyst levels is 0.5g.Be reflected under the downflow mode and carry out.Transforming degree can the temperature when reacting be regulated.The catalyzer that carries out this test is made up of pure zeolite and the platinum of 0.5 weight % through granulation.
Molecular sieve comprises at least a hydrogenation-dehydrogenation element usually, for example at least a group VIII metal, the preferred at least a metal that is selected from Pt or Pd, this metal is introduced in the molecular sieve by dry impregnation or ion-exchange, or uses other technology that well known to a person skilled in the art.
In the gross weight of used molecular sieve, to express with weight %, the content of the hydrogenation-dehydrogenation metal of being introduced is generally less than 5% (0.01-5%), preferably less than 1% (0.01-1%), is about 0.5% usually.Under these conditions, the transformation efficiency that molecular sieve of the present invention will produce n-heptadecane is 95 weight % (transformation efficiency is subjected to temperature regulation), is 70 weight % or bigger to the selectivity of isomerization product, preferably at least 80 weight %.
At standard n-heptadecane isomerization test (SIT
N-c17) in isomerization selectivity definition be:
The transformation efficiency that obtains n-heptadecane thus is 95%.
C
17-product is to comprise the compound that is less than 17 carbon atoms, does not consider its branch degree.
When handling actual charging, at first form molecular sieve of the present invention.In first kind of scheme, can on molecular sieve, deposit at least a group VIII metal, preferred Pt and Pd can use the method for well known to a person skilled in the art to carry out.Particularly, can be generally unbodied matrix and mix with a kind of, as with wet oxidation alumina gel powder mixes.Then, for example extrude this mixture of plate extrusion molding by one.In mixture total weight amount (molecular sieve+matrix), the content of molecular sieve is generally 0.5-99.9% in the mixture that obtains, preferred 10%-90%, more preferably 20%-70%.
Hereinafter, term " carrier " is used for representing the mixture of molecular sieve+matrix.
Moulding also can be adopted other matrix outside the alumina, as: magnesium oxide, amorphous silicas-aluminum oxide, natural clay (kaolin, wilkinite, sepiolite, attapulgite) also can adopt other technology to carry out moulding, as granulation or ball milling granulating.
Can adopt to well known to a person skilled in the art that be the group VIII metal with the method for metal deposition on molecular sieve with metal hydride, preferred Pt and/or Pd are deposited on the carrier.Competitive cationic exchange technology also can be used, and wherein, it is about 20 that the preferred ammonium nitrate of competitor (competitor), competition ratio are at least, preferably about 30-200.When using Pt or Pd, use tetramine platinum (Platinum tetramine) title complex or tetramine palladium complex usually, can deposit on the molecular sieve fully during their actual uses.This cationic exchange technology also can with metal is directly deposited on the molecular sieve before matrix is mixed.
After group VIII metal (or several metal) deposition, carry out calcination step usually, calcination is in air or oxygen, carries out 0.5-10 hour under 300 ℃-600 ℃, preferably carries out 1-4 hour under 350 ℃-550 ℃.In hydrogen, reduce subsequently, generally under 300 ℃-600 ℃ of temperature, carried out 1-10 hour; Preferably under 350 ℃-550 ℃, carried out 2-5 hour.
Platinum and/or palladium can directly not deposit on the molecular sieve yet, but can deposit on the aluminum oxide wedding agent, promptly before moulding or after the moulding, finish by carrying out anionresin with chloroplatinic acid, the acid of chlordene palladium and/or Palladous chloride in the presence of the competitor example hydrochloric acid.Usually, deposited platinum and/or palladium after, catalyzer carries out calcination as previously mentioned, and reduces in hydrogenation.
Advantageously, the charging of adopting the inventive method to handle is the cut with high relatively pour point, and the cut of this high pour point is to wish to reduce its pour point value.
Method of the present invention can be used for handling various chargings, from relative lighter cut such as kerosene and jet fuel, to charging with higher such as middle distillate, vacuum residuum, gas oil, from the middle distillate (LCO and HCO) of FCC with add hydrogenolysis residual oil.
The charging that desire is handled is generally initial boiling point greater than about 175 ℃ C10+ cut, or and initial boiling point greater than 315 ℃ C20+ cut, the last running that preferred initial boiling point is at least 380 ℃.Method of the present invention is specially adapted to the processing of paraffinic hydrocarbons overhead product such as middle distillate, and said middle distillate comprises gas oil, kerosene, jet fuel and other cut, and wherein the pour point of these cuts and viscosity should be within aforesaid scopes.
The charging that can adopt the inventive method to handle can comprise paraffinic hydrocarbons, alkene, naphthenic hydrocarbon, aromatic hydrocarbons and heterogeneous ring compound, and most of high-molecular weight n-paraffin and very slight ramose high molecular weight paraffinic.
The reaction of carrying out should make the degree of cracking reaction keep quite low so that this method from considering to have vitality economically.The degree of cracking reaction is usually less than 20 weight %.
Its pour point of typical feed that can advantageously handle according to the present invention is preferably greater than 15 ℃ usually greater than 0 ℃.The pour point of handling the product obtain according to the inventive method is less than 0 ℃, preferably less than-10 ℃ approximately.
These chargings comprise more than 30% until up to about 90%, the high molecular n-paraffin that is higher than 90 weight % in some cases, this paraffinic hydrocarbons comprises and surpasses 10 carbon atoms, and very slight ramose is the paraffinic hydrocarbons that surpasses 10 carbon atoms that contains of high molar weight simultaneously.When said ratio was at least 60 weight %, this method was even more important.
The non-limiting example of the charging that other available the present invention handles comprises lubricating oil, from the synthetic paraffinic hydrocarbons of Fischer, Tropsch method, have the poly-alpha olefins of high pour point, synthetic wet goods.This method also can be used for other and comprises the compound of nalka hydrocarbon chain as defined above, for example, and nalka basic ring alkane compound, or comprise the compound of at least one aryl.
The operational condition of implementing hydrogenation isomerization reaction of the present invention is as follows: temperature of reaction is 170 ℃-500 ℃, preferred 180 ℃-450 ℃, is preferably 180 ℃-400 ℃; Pressure is the 1-250 crust, preferred 10-200 crust; Hourly space velocity (vvh, the per hour feed volume that adds under the unit catalyst volume) is about 0.05h
-1-100h
-1, preferably about 0.1h
-1-30h
-1
Charging contacts in the presence of hydrogen with catalyzer.Represent the consumption of hydrogen with L hydrogen/L charging, the consumption of hydrogen is the about 2000L hydrogen of 50-/L charging, preferred 100-1500L hydrogen/L charging.
The concentration of contained nitrogen compound is preferably less than about 200ppm (weight), preferably less than l00ppm (weight) in the charging that desire is handled.Sulphur content preferably less than 500ppm (weight), is preferably less than 200ppm (weight) less than 1000ppm (weight).The concentration of metal in charging such as Ni or V is extremely low, promptly less than 50ppm (weight), preferably less than 10ppm (weight), is preferably less than 2ppm (weight).
Compound obtained by the method for the present invention is gone up substantially and is methyl list branch, two branches and multiple-limb compound.For example, by pure heptadecane (n-C
17) charging that constitutes optionally obtains methyl n-Hexadecane compound when implementing method of the present invention, is mainly 2-methyl n-Hexadecane, also comprises two branch's compounds 2,7-; 2,8-; 2,9-; 2, l0-; And 2,11-dimethyl pentadecane.Total isomerized product accounts for more than the 70 weight % that obtain product, and transformation efficiency is 95%.Isomerized carbon atom can separate by the wide distance of bridge at least.
The following example is used to illustrate the present invention, but is not the qualification to protection domain of the present invention.They are that (the standard isomerization test, SIT) charging of Gou Chenging or hydrocracking residual oil experimentize by n-heptadecane in employing.
Embodiment 1, catalyzer Cl (catalyzer of the present invention)
Raw material is a H type NU-10 zeolite, and total Si/Al ratio is about 30, and the hole opening is limited to 10 Sauerstoffatoms, and bridge is wide, and promptly two hole aperture pitch are 0.55nm.The crystal grain of Nu-10 zeolite is aciculiform, and length is less than 1 μ m, and width is 0.1 μ m-0.4 μ m.
With NU-10 zeolite [Pt (NH
3)
4] Cl
2Solution is done dipping, after 450 ℃ of following calcination and reduction, obtains being carried on the platinum catalyst on the zeolite, and Pt content is 0.5 weight %.
The zeolite 0.5g that carries platinum is carried out granulation (200 μ m-300 μ m particle), introduce in the fixed-bed reactor.
At hydrogen dividing potential drop 150KPa, n-heptadecane dividing potential drop 0.5KPa carries out standard n-heptadecane isomerization test (SIT) under the total pressure 150.5KPa, and this test is carried out in fixed bed, and the constant flow rate of n-heptadecane is 15.4ml/h, and catalyst levels is 0.5g.Adjust transforming degree by temperature of reaction.
In this embodiment, the temperature that makes the transformation efficiency of n-heptadecane reach 95 weight % is 190 ℃.Under this temperature, the selectivity of isomerization product is 93 weight %.This selectivity definition is as follows: isomerization selectivity (%)=
The selectivity of single branch compound is 67.4%, and the selectivity of multiple-limb compound is 25.6%.
Embodiment 2: catalyzer C2 (non-the present invention)
Raw material is a H type USY zeolite, and total Si/Al ratio is about 5, and the hole opening is limited to 12 Sauerstoffatoms, and bridge is wide, and promptly two hole aperture pitch are 0.7nm.
With USY-H zeolite [Pt (NH
3)
4] Cl
2Solution is done dipping, after 450 ℃ of following calcination and reduction, obtains being carried on the platinum catalyst on the zeolite, and Pt content is 0.5 weight %.
The zeolite 0.5g that carries platinum is selected grain (200 μ m-300 μ m particle), introduce in the fixed-bed reactor.
At hydrogen dividing potential drop 150KPa, n-heptadecane dividing potential drop 0.5KPa promptly carries out standard n-heptadecane isomerization test (SIT) under the total pressure 150.5KPa, and this test is carried out in fixed bed, and the constant flow rate of n-heptadecane is 15.4ml/h, and catalyst levels is 0.5g.Adjust transforming degree by temperature of reaction.
In this embodiment, the temperature that makes the transformation efficiency of n-heptadecane reach 95 weight % is 220 ℃.Under this temperature, the selectivity of isomerization product only is 16 weight %.The selectivity definition is as embodiment 1.
Therefore, the standard isomerization test is the method for selecting catalyst.
Embodiment 3: the present invention
The zeolite that is used for present embodiment is the NU-10 zeolite identical with embodiment 1.
The zeolite SB3 type alumina lap that provides by Condea.Mashed prod after the grinding is extruded by the extrusion plate of 1.2mm diameter.[Pt (NH is used in extrudate 500 ℃ of following calcination 2 hours in air then
3)
4] Cl
2Do dipping, 550 ℃ of following calcination in air again.Platinum content among the last catalyzer C3 is 0.7 weight %, and in total catalyst weight, the content of zeolite is 60 weight %.
Catalyzer C3 is at the hydrocracking from underpressure distillation
The evaluation feedstock characteristic of effect in the hydrogenation isomerization reaction that residual oil carries out:
| Sulphur content (ppm (weight)) | 12 |
| Nitrogen content (ppm (weight)) | 2 |
| Pour point (℃) | +30 |
| Initial boiling point | 104 |
| 5％ | 325 |
| 10％ | 385 |
| 50％ | 452 |
| 90％ | 520 |
| 95％ | 536 |
| Terminal point | 573 |
The catalyzer that makes is used for preparing lube stock by the hydrogenation isomerization to above-mentioned charging.
Before catalytic test, at first the scene makes catalyzer 450 ℃ of reduction down in reactor.Reduction process divides several steps to carry out, and comprising: 150 ℃ following 2 hours, with 1 ℃/min elevated temperature to 450 ℃, then 450 ℃ following 2 hours.In reduction process, hydrogen flow rate is 1000L H
2/ 1L catalyzer.
Reaction is carried out under the following conditions: 300 ℃ of temperature, stagnation pressure 12MPa, hourly space velocity 0.9h
-1, hydrogen flow rate 1000L H
2/ L charging.Under these reaction conditionss, total transformation efficiency of 400-is 65%, and the efficient of lube stock is 86%.
The characteristic of isomerization oil is as follows:
| Viscosity index VI | 136 |
| Pour point | -18 |
| Oil/charging yield (% (weight)) | 86 |
This embodiment has shown the importance of using catalyzer of the present invention, and it can reduce the pour point of the initial charge that is used for hydrocracking residual oil, keeps high viscosity index (HVI) (VI) simultaneously again.
The objective of the invention is to produce a kind of oil, also can reach other purpose simultaneously.In a word, the present invention can be used for producing multiple, localized branching product.
Claims (24)
1 one kinds will comprise that at least one compound that contains the above straight-chain paraffin chain of 10 carbon atoms carries out the isomerized method of selective hydrogenation, the compound that desire is handled contacts with a kind of catalyzer, said catalyzer comprises at least a hydrogenation-dehydrogenation element and at least a molecular sieve with one dimension or two-dimentional hole pattern, wherein the opening in enterable hole is limited to 10 Sauerstoffatoms, be defined as distance between the Kong Yukong of bridge width less than 0.70nm, wherein said molecular sieve comprises boron in zeolite framework, iron, gallium and/or zinc atom, and, when the isomerization test of the n-heptadecane of carrying out standard, selectivity of catalyst is at least 70%, and the transformation efficiency of isomerization product is 95%.
2 according to the process of claim 1 wherein that the bridge width is 0.50nm-0.68nm.
3 methods according to claim 1 or 2, its jackshaft width is 0.52nm-0.65nm.
4 according to the process of claim 1 wherein that the grain-size of molecular sieve is less than 2 μ m.
5 according to the process of claim 1 wherein that the grain-size of molecular sieve is less than 1 μ m.
6 according to the process of claim 1 wherein that the grain-size of molecular sieve is less than 0.4 μ m.
7 according to the process of claim 1 wherein that molecular sieve is NU-10.
8 according to the process of claim 1 wherein that molecular sieve is NU-23.
9 according to the process of claim 1 wherein that molecular sieve is NU-87.
10 according to the process of claim 1 wherein that molecular sieve is Theta-1.
11 according to the process of claim 1 wherein that molecular sieve is EU-13.
12 according to the process of claim 1 wherein that hydrogenation one dehydrogening element is selected from group VIII metal, group vib metal, rhenium and niobium.
13 according to the process of claim 1 wherein catalyzer comprise a kind of matrix, in the molecular sieve of matrix and molecular sieve mixture 0.5-99.9 weight %, and in the hydrogenation-dehydrogenation metal of molecular sieve less than 5 weight %.
14 methods according to claim 13, wherein catalyzer comprises the molecular sieve in matrix and molecular sieve mixture 10 weight %-90 weight %.
15 according to the process of claim 1 wherein that pressure is the 1-250 crust, and temperature is 170 ℃-500 ℃, and hourly space velocity is 0.05h
-1-100h
-1, be 50L-2000L hydrogen/L charging with the consumption of L hydrogen/hydrogen that the L charging is represented.
16 methods according to claim 15, wherein temperature is 180-450 ℃.
17 methods according to claim 15, wherein pressure is the 10-200 crust.
18 methods according to claim 15, wherein the consumption of hydrogen is 100L-1500L hydrogen/L charging.
19 according to the process of claim 1 wherein that the compound that desire is handled is selected from normal alkane, positive alkyl naphthene and comprise the compound of at least one aryl.
20 according to the process of claim 1 wherein that the compound that desire is handled has been present in initial boiling point greater than in 175 ℃ the charging.
21 according to the process of claim 1 wherein that the compound that desire is handled has been present in initial boiling point at least greater than in 380 ℃ the charging.
22 according to the process of claim 1 wherein that the compound that desire is handled comprises a nalka hydrocarbon chain that contains 15-50 carbon atom.
23 according to the process of claim 1 wherein that the compound that desire is handled comprises a nalka hydrocarbon chain that contains 15-40 carbon atom.
24 methods according to claim 1, wherein the compound of desire processing is present in a kind of hydrocarbon charging, and this charging is selected from middle distillate, vacuum residuum, hydrocracking residual oil, the paraffinic hydrocarbons from the Fischer-Tropsch method, synthetic oil, gas oil fraction, the middle distillate from FCC, lube stock and poly-alpha olefins.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96121074A CN1090159C (en) | 1996-10-27 | 1996-10-27 | Process for selective hydroisomerisation of long linear and/or slightly branched paraffins using catalyst based on molecular sieve |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96121074A CN1090159C (en) | 1996-10-27 | 1996-10-27 | Process for selective hydroisomerisation of long linear and/or slightly branched paraffins using catalyst based on molecular sieve |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1180686A CN1180686A (en) | 1998-05-06 |
| CN1090159C true CN1090159C (en) | 2002-09-04 |
Family
ID=5126753
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96121074A Expired - Fee Related CN1090159C (en) | 1996-10-27 | 1996-10-27 | Process for selective hydroisomerisation of long linear and/or slightly branched paraffins using catalyst based on molecular sieve |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1090159C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110578057B (en) * | 2019-09-16 | 2020-08-04 | 中国原子能科学研究院 | Preparation method of diluent for spent fuel aftertreatment |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0065400A2 (en) * | 1981-05-20 | 1982-11-24 | Imperial Chemical Industries Plc | Zeolites |
| US4717465A (en) * | 1984-12-31 | 1988-01-05 | Mobil Oil Corporation | Process for producing jet fuel with ZSM-22 containing catalist |
| WO1992001657A1 (en) * | 1990-07-20 | 1992-02-06 | Chevron Research And Technology Company | Use of modified 5-7 å pore molecular sieves for isomerization of hydrocarbons |
-
1996
- 1996-10-27 CN CN96121074A patent/CN1090159C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0065400A2 (en) * | 1981-05-20 | 1982-11-24 | Imperial Chemical Industries Plc | Zeolites |
| US4717465A (en) * | 1984-12-31 | 1988-01-05 | Mobil Oil Corporation | Process for producing jet fuel with ZSM-22 containing catalist |
| WO1992001657A1 (en) * | 1990-07-20 | 1992-02-06 | Chevron Research And Technology Company | Use of modified 5-7 å pore molecular sieves for isomerization of hydrocarbons |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1180686A (en) | 1998-05-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101968323B1 (en) | CATALYTIC PROCESSES AND SYSTEMS FOR BASE OIL PRODUCTION USING ZEOLITE SSZ-32x | |
| JP2907543B2 (en) | Isomerization of waxy lubricating oils and petroleum waxes using silicoaluminophosphate molecular sheep catalysts | |
| KR101905476B1 (en) | Catalytic processes and systems for base oil production from heavy feedstock | |
| US5614079A (en) | Catalytic dewaxing over silica bound molecular sieve | |
| JP3839848B2 (en) | Catalytic dewaxing process and catalyst composition | |
| KR100449389B1 (en) | Method for selective hydrogenation isomerization of high-grade paraffins having straight chain and / or few branching chains using molecular sieve catalysts | |
| CN1221500C (en) | Selective hydrogenation isomerizating process for chain paraffins | |
| CA2801718C (en) | Catalytic processes and systems for base oil production from light feedstock | |
| EP3215267B1 (en) | Base stock production using a high activity catalyst | |
| JP2003525118A (en) | Zeolite ZSM-48 based catalyst and method for improving pour point of paraffin charge | |
| CA2831435C (en) | Novel process and catalyst system for improving dewaxing catalyst stability and lubricant oil yield | |
| EP0536325B2 (en) | Wax isomerization using catalyst of specific pore geometry | |
| KR20070008737A (en) | Eu-1 zeolite catalyst and a process for improving the pour point of feeds contatining paraffins | |
| CN1090159C (en) | Process for selective hydroisomerisation of long linear and/or slightly branched paraffins using catalyst based on molecular sieve | |
| CN1098334C (en) | Method for improving pour-point of paraffin feedstock with Nu-86 zeolite based catalyst | |
| KR100546454B1 (en) | NU-85 Zeolite Catalyst and How to Use It to Improve the Pour Point of Paraffin-Containing Feedstock | |
| FR2951192A1 (en) | PROCESS FOR THE PRODUCTION OF MEDIUM DISTILLATE FROM FISCHER TROPSCH WAXES USING A MODIFIED ZEOLITHE CATALYST | |
| CN1703492A (en) | Enhanced lube oil yield by low or no hydrogen partial pressure catalytic dewaxing of paraffin wax | |
| FR2738243A1 (en) | Hydro-isomerising straight and/or slightly branched long chain hydrocarbon(s) | |
| JP2016084474A (en) | Novel process and catalyst system for improving dewaxing catalyst stability and lubricant oil yield | |
| FR2756295A1 (en) | Improving flowing point of paraffin feed with zeolite based catalyst | |
| FR2738244A1 (en) | Hydro-isomerising straight and/or slightly branched long chain hydrocarbon(s) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20020904 Termination date: 20111027 |