CN100395220C - Method for isomerization of light hydrocarbon - Google Patents
Method for isomerization of light hydrocarbon Download PDFInfo
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- CN100395220C CN100395220C CNB2005100597615A CN200510059761A CN100395220C CN 100395220 C CN100395220 C CN 100395220C CN B2005100597615 A CNB2005100597615 A CN B2005100597615A CN 200510059761 A CN200510059761 A CN 200510059761A CN 100395220 C CN100395220 C CN 100395220C
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Abstract
The present invention relates to a method for isomerizing light hydrocarbons. The method comprises: raw materials of the light hydrocarbons are rectified for eliminating trace water and isopentane in the raw materials; subsequently, hydroisomerization reaction is carried out to the raw materials of light hydrocarbons without water and isopentane under the existence of catalysts (namely solid super acid), wherein the catalysts (namely solid super acid) comprise zirconium dioxide of supported sulfate radicals. The method can improve the activity of the catalysts (namely solid super acid) and can improve the yield of isoparaffin.
Description
Technical field
The present invention is a kind of isomerization method of light hydrocarbons, specifically, be a kind of be the isomerization method for light hydrocarbon of catalyzer with the solid super-strong acid.
Background technology
Light hydrocarbon isomerization is one of important process of exploitation clean fuel, and its used catalyzer mainly is divided into three kinds: molecular sieve catalyst, solid super acid catalyst and halogen-containing aluminium oxide catalyst, but the equal carried noble metal component of described catalyzer.Adopt halogen-containing aluminium oxide catalyst to carry out light hydrocarbon isomerization,, can cause equipment corrosion and environmental pollution in reaction process because the halogen in the aluminum oxide more easily runs off.For preventing that halogen runs off in the catalyzer, very harsh to the requirement of the water-content in the raw material, also need mend chlorine at any time in the running, to keep the due acidity of catalyzer.Therefore use technical process complexity, the investment of this kind catalyzer big.Adopt the isomerization process of molecular sieve catalyst, flow process is simple, to the requirement of stock oil foreign matter content also broad, is used widely industrial at present.But this type of catalyst activity is lower, and the halogen-containing relatively aluminium oxide catalyst of isomerization reaction temperature is higher, and the octane value of isomerization product is also lower.Solid super acid catalyst is owing to have stronger acidity, the isomerization activity height, thereby can carry out isomerization reaction at a lower temperature, obtain higher isomerization rate.In addition, there is not the halogen losing issue in solid super acid catalyst, thereby can not cause corrosion and environmental pollution to equipment in the reaction process.At present, the solid super-strong acid that is used for light hydrocarbon isomerization reaction mainly is to adopt SO
4 2-/ ZrO
2Be carrier, and the catalyzer of supported V III family precious metal formation, be a kind of solid acid catalyst (K.Arata, Adv.Catal, 37 (1990) 165) with applications well prospect.
It is the isomerization method for light hydrocarbon of catalyzer that CN1324392A discloses a kind of solid super-strong acid that adopts, this method is reduced to the moisture content in the raw material below the 5wppm, it is contacted with solid super acid catalyst carry out isomerization reaction, improve activity of such catalysts and selectivity with this.The method of this method employing absorption removes the water in the raw material, the preferred A type molecular sieve of sorbent material that dewaters used.
CN1345913A discloses a kind of method for hydroisomerization of light hydrocarbon, and this method is used the molecular sieve catalyst that contains β zeolite and mordenite, carries out C under 200～400 ℃ comparatively high temps
5, C
6The light hydrocarbon isomerization reaction.For improving the isomerization rate of raw material, this method is gone out the too much isopentane separation that contains in the raw material earlier by rectifying, carries out isomerization reaction again, thereby has improved the yield of isomerized products in the resultant of reaction effectively.
Summary of the invention
The purpose of this invention is to provide a kind of solid super-strong acid that adopts is the isomerization method for light hydrocarbon of catalyzer, and this method can effectively improve described activity of such catalysts, and suitably improves the productive rate of isoparaffin, increases the octane value of isomerization product.
Isomerization method for light hydrocarbon provided by the invention, comprise that described light hydrocarbon feedstocks is carried out rectifying removes wherein minor amount of water and iso-pentane, the light hydrocarbon feedstocks that will remove then behind water and the iso-pentane carries out hydroisomerization reaction in the presence of solid super acid catalyst, described solid super acid catalyst comprises the zirconium dioxide of sulfur loaded acid group.
The inventive method removes minor amount of water in the light hydrocarbon feedstocks earlier with rectification method, water-content is reduced to appropriate value, iso-pentane in the while separate raw materials, thereby can improve the activity of solid super acid catalyst, and make and contain more Skellysolve A in the isomerization raw material, thereby improve the isomerization rate of normal alkane isomerization reaction, improve the octane value of isomerization product.
Description of drawings
Fig. 1 is the schematic flow sheet of the inventive method.
Embodiment
The inventive method removes the minor amount of water that wherein contains with light hydrocarbon feedstocks with rectificating method earlier, so that the water-content in the isomerization raw material reduces, improves the catalytic activity of solid super acid catalyst.In rectifying and dewatering, also remove the iso-pentane in the raw material, make that isopentane content significantly reduces in the raw material, thereby effectively improve the isomerization rate of Skellysolve A in the raw material, improve the octane value of isomerization product.
Remove the light hydrocarbon feedstocks behind water and the iso-pentane in the described method, be that water-content in the isomerization raw material is preferably less than 15ppm, more preferably 5～15ppm is preferably 5～10ppm, and isopentane content is not more than 20 quality % of light hydrocarbon feedstocks iso-pentane total content in the described isomerization raw material.
The described isomerization raw material that removes behind water and the iso-pentane carries out isomerization reaction facing under the hydrogen state to contact with solid super acid catalyst.Suitable isomerisation conditions is that 100～250 ℃, 0.5～3.0MPa, hydrogen/hydrocarbon molecule ratio are 0.1～6.0, isomerization raw material volume space velocity 1.0～4.0 hours
-1Preferred temperature of reaction is 130～200 ℃, and pressure is that 1.5～2.0MPa, hydrogen/hydrocarbon molecule ratio are 1.5～3.0.
The inventive method removes minor amount of water and the iso-pentane in the light hydrocarbon feedstocks in rectifying tower, control rectifying tower tower top temperature is 65～75 ℃ during operation, and column bottom temperature is 115～125 ℃, and pressure tower is 0.45～0.55MPa.
The isomerization raw material that will remove in the described method behind water and the iso-pentane carries out hydroisomerization reaction, after the reaction with hydrogen with after isomerization reaction product separates, recycle.On the described recycle hydrogen pipeline drying and dehydrating device is set, in circulating hydrogen, accumulates with the minor amount of water that prevents to exist in the raw material in the reaction process.The preferred A type molecular sieve of siccative or the aluminum oxide of filling in the described drying and dehydrating device are as 3A, 4A or 5A molecular sieve.The water-content of circulating hydrogen is controlled at below the 30ppm, is preferably 1.0～10ppm.
Described hysomer product is after gas-liquid separation, and hydrogen is used for circulation, and carburet hydrogen is discharged system, and product liquid mixes as isomerization product with the iso-pentane that light hydrocarbon feedstocks rectifying removes.
The VIII family metal that also contains 0.5～5.0 quality % in the solid super acid catalyst of the present invention, the preferred platinum of VIII family metal, rhodium or palladium, more preferably platinum.Sulphur content is 0.5～5.0 quality % in the catalyzer.Zirconium dioxide in the solid super acid catalyst can be pure cubic phase, also can be four directions and monocline mixing mutually.Preferred 5～70 quality % of monocline phase content in the zirconium dioxide of mixed phase.
Above-mentioned Preparation of catalysts method comprises that with concentration be the sulfuric acid of 0.1～3.0mol/L or the aqueous solution dipping zirconium dioxide of ammonium sulfate, and dry then and roasting makes the zirconium dioxide of sulfur loaded acid group, is solid super-strong acid.For preventing described solid super-strong acid carbon distribution in isomerization reaction, preferably with described solid super-strong acid with VIII family metallic compound dipping, Gu liquid during dipping/than being 0.4～4.0: 1, preferred 0.6～2.0: 1, dry 500～700 ℃ of roastings in back, preferred 2～6 hours of roasting time.The used acid of the preferred chlorine palladium of VIII family metallic compound, Platinic chloride or the ammonium chloroplatinate of preparation steeping fluid.
Described zirconium dioxide can adopt any known method preparation, preferably adopts following method preparation:
(1) the soluble zirconium salts solution is contacted with alkaline solution, making the pH value is 1.2～13.5, generates the hydrous oxide of zirconium,
(2) with above-mentioned hydrous oxide 50～200 ℃ of hydrothermal treatment consists 0.5～20 hour,
(3) filter and washing until filtrate pH value be 7 and filtrate in do not contain Cl
-, it is dry then,
In the aforesaid method, (1) step is the hydrous oxide of preparation zirconium, i.e. zirconium hydroxide hydrogel, and used solubility zirconates is selected from zirconium oxychloride, zirconium nitrate or zirconium sulfate, the preferred oxygen zirconium chloride, the preferred ammoniacal liquor of alkaline solution, its concentration is 5～28 heavy %.The pH value of the hydrous oxide control of preparation zirconium is preferred 7～12, promptly is controlled at formation zirconium hydroxide hydrogel alkaline environment under.The raw material addition sequence can be that alkaline solution is joined in the zirconium salt solution, also zirconates can be joined in the alkaline solution, and the concentration of used zirconates is 5～50 heavy %, preferred 10～25 heavy %.
Described (2) step is that the zirconium hydroxide hydrogel is carried out hydrothermal treatment consists, should in airtight autoclave pressure, carry out, the mode of handling is that the zirconium hydroxide hydrogel is placed for some time under described temperature, preferred 70～130 ℃ of hydrothermal treatment consists temperature, preferred 10～20 hours of storage period.Can stir in the put procedure, also can not stir.
Described (3) step is that the zirconium hydroxide after the hydrothermal treatment consists is washed and drying, and drying temperature is 60～200 ℃, preferred 100～120 ℃; 2～24 hours time of drying, preferred 12～24 hours.
The light hydrocarbon feedstocks that is applicable to the inventive method is the light naphthar that produces in straight run or the secondary processing process.Preferred C
4～C
7Light hydrocarbon component, comprise alkane, naphthenic hydrocarbon, aromatic hydrocarbons.More preferably C
5～C
6Light hydrocarbon component, wherein the content of normal paraffin is 20～80 quality %.
Describe the present invention in detail below in conjunction with accompanying drawing.The light hydrocarbon feedstocks that contains minor amount of water among Fig. 1 enters rectifying tower 1 by pipeline 8, the control tower top temperature is 65～75 ℃, and column bottom temperature is 115～125 ℃, and pressure tower is 0.45～0.55MPa, most of iso-pentane and water contained in the light hydrocarbon feedstocks distillate from cat head, mainly contain Skellysolve A and C in the tower bottom distillate
6Hydrocarbon, water-content is reduced to 5～15ppm, for having removed the isomerization raw material of minor amount of water and iso-pentane.Tower bottom distillate is discharged by pipeline 11 and is entered process furnace 2 after circulating hydrogen from pipeline 10 mixes, and enters reactor 3 after being heated to preset temperature, and reactor can be arranged to one or two placed in-line reactors, between two reactors the heat-obtaining device should be set.The heat-obtaining device can be interchanger or liquid hydrogen injection.The isomerization reaction resultant enters high-pressure separator 4 through heat exchange cooling back by pipeline 12.Hydrogen separates with liquid product in high-pressure separator 4, and recycles from top by pipeline 14 discharges, and liquid product enters stabilizer tower 5 by pipeline 13.Because the amounts of hydrogen that isomerization reaction consumes is seldom, only need to replenish and the emptying small quantity of hydrogen, so the stock oil minor amount of water of bringing into, can be in system's internal recycle accumulation.The circulating hydrogen that comes out of high-pressure separator preferably through after 6 dehydrations of drying and dehydrating jar, is squeezed into pipeline 10 by recycle compressor 9 again and is recycled for this reason.The water-content of circulating hydrogen is controlled at below the 30ppm, preferably at 1.0～10ppm.The light constituent that discharge at stabilizer tower 5 tops is discharged reactive system by pipeline 17, and component is mixed the back by pipeline 16 discharges with the component that rectifying tower top pipeline 15 is discharged at the bottom of the tower, is high-octane isomerization product.
Below by example in detail the present invention, but the present invention is not limited to this.
Example 1
The preparation solid acid catalyst.
Get 100 gram zirconium oxychloride (ZrOCl
28H
2O), the adding appropriate amount of deionized water is made into the aqueous solution of 25 quality %, strong aqua to the pH value that drips 25 quality % is 10, the zirconium hydroxide hydrogel that generates is transferred to good seal in the autoclave pressure, 90 ℃ of hydrothermal treatment consists 20 hours, washing also is filtered to filtrate for neutral and can not detect chlorion, with solid 110 ℃ of dryings 48 hours.Get 10 gram grind into powders, add the sulfuric acid of 8 milliliters of 1mol/L, room temperature was placed 1 hour, 110 ℃ of dryings 24 hours.With platinum content is the H of 3.77 mg/ml
2PtCl
66.4 milliliters of solution dipping 1 hour, 110 ℃ of dryings 12 hours, 600 ℃ of roastings made catalyst A in 4 hours, and wherein the existing monocline of zirconium white has cubic phase mutually again.Monocline phase ratio sees Table 1 in the active component content of catalyst A and the zirconium white.
Example 2
Method by example 1 prepares catalyst B, and the pH that controls during the hydrogel of different is preparation zirconium hydroxide is 8.5, and the hydrothermal treatment consists time is 6 hours.The existing monocline of zirconium white has cubic phase again mutually in the catalyst B, and monocline phase ratio sees Table 1 in its active component content and the zirconium white.
Example 3
Method by example 1 prepares catalyzer C, different is add strong aqua to pH be 12, then with the zirconium hydroxide hydrogel that generates 150 ℃ of hydrothermal treatment consists 20 hours.The existing monocline of zirconium white has cubic phase again mutually among the catalyzer C, and monocline phase ratio sees Table 1 in its active component content and the zirconium white.
Example 4～6
Press the flow process of Fig. 1, with C
5～C
6Light hydrocarbon feedstocks earlier removes wherein minor amount of water and iso-pentane with rectifying tower.Various hydrocarbon contents are in the described raw material: C
5Alkane 53.1 quality %, C
6Alkane 32.1 quality %, C
6Naphthenic hydrocarbon 6.5 quality %, benzene 1.0 quality %, water-content is 35ppm in the raw material, and sulphur content is 0.5ppm, and concrete hydrocarbon composition and research octane number (RON) (RON) see Table 2.70 ℃ of control rectifying tower tower top temperatures, 120 ℃ of column bottom temperatures, pressure 0.5MPa, the hydrocarbon of cat head and tower bottom distillate is formed and research octane number (RON) RON sees Table 2, and the water-content of fraction is reduced to 5.2ppm at the bottom of the tower.
Tower bottom distillate is sent into the fixed bed high pressure reaction assembly, and the catalyst reactor loading amount is 50 milliliters (51.0 grams), at 180 ℃, 1.8MPa, and feed volume air speed 2.5 hours
-1Hydrogen/hydrocarbon molecule is than being reaction 20 hours under 2.0 the condition, reaction product cooling back is analyzed by gas-chromatography, filling 3A molecular sieve in the drying and dehydrating jar 6 on the circulating hydrogen pipeline, dehydration back recycle hydrogen water-content is 6ppm, and the hydrocarbon of the used isomerization catalyst of each example, isomerization product is formed and octane value RON sees Table 3.
Example 7
The method of pressing example 4 is earlier with C
5～C
6Light hydrocarbon feedstocks carries out isomerization reaction after removing water and iso-pentane again, and the water-content of different is control rectifying tower tower bottom distillate is 8.5ppm, and reaction result sees Table 3.
Comparative Examples
The method of pressing example 4 is to C
5～C
6Lighter hydrocarbons carry out isomerization, and different is that raw material removes moisture and iso-pentane without rectifying tower, directly feed reactor and carry out isomerization reaction, and the hydrocarbon of isomerization product is formed and octane value RON sees Table 3.
By table 3 data as can be known, carry out the lighter hydrocarbons isomerization reaction with the inventive method, than the Comparative Examples method, the isoparaffin of gained isomate increases, and octane value improves.
Table 1
| The catalyzer numbering | Platiniferous, quality % | Sulfur-bearing, quality % | ZrO 2The oblique crystal ratio, quality % |
| A | 0.30 | 1.58 | 15 |
| B | 0.36 | 1.33 | 5 |
| C | 0.31 | 1.43 | 52 |
Table 2
| Component | Raw material hydrocarbon is formed, quality % | The overhead fraction hydrocarbon is formed, quality % | The tower bottom distillate hydrocarbon is formed, quality % |
| C 4 | 4.3 | 13.6 | |
| Iso-pentane | 27.9 | 73.4 | 6.2 |
| Skellysolve A | 28.2 | 13.0 | 35.4 |
| 2, the 2-dimethylbutane | 1.0 | 1.5 | |
| 2, the 3-dimethylbutane | 5.0 | 7.4 | |
| 2 methylpentanes | 10.4 | 15.3 | |
| 3 methylpentanes | 5.6 | 8.3 | |
| Normal hexane | 10.1 | 14.9 | |
| Methylcyclopentane | 4.9 | 7.2 | |
| Benzene | 1.0 | 1.5 | |
| Hexanaphthene | 1.6 | 2.3 | |
| RON | 73.6 | 90.4 | 69.3 |
Table 3
| Instance number | Example 4 | Example 5 | Example 6 | Example 7 | Comparative Examples |
| Catalyst system therefor | A | B | C | A | A |
| The isomerization product hydrocarbon is formed, quality % C 4Iso-pentane Skellysolve A 2,2-dimethylbutane 2,3-dimethylbutane 2 methylpentanes 3 methylpentane normal hexane methylcyclopentane cyclohexans | 6.9 43.2 9.8 9.6 3.8 12.2 7.4 5.4 1.2 0.1 0.4 | 6.1 43.5 9.9 9.7 3.8 12.4 7.3 5.6 1.2 0.1 0.4 | 6.8 41.9 11.1 8.1 3.7 12.5 8.0 6.2 1.1 0.1 0.5 | 6.2 42.7 10.3 9.1 3.9 12.5 7.6 5.9 1.3 0.1 0.4 | 5.7 35.5 17.5 6.9 3.4 14.1 7.6 6.2 2.1 0.1 0.9 |
| RON | 85.0 | 84.8 | 83.9 | 84.4 | 80.4 |
Claims (12)
1. isomerization method for light hydrocarbon, comprise that described light hydrocarbon feedstocks is carried out rectifying removes wherein minor amount of water and iso-pentane, make that water-content is less than 15ppm in the light hydrocarbon feedstocks that removes behind water and the iso-pentane, wherein isopentane content is not more than 20 quality % of light hydrocarbon feedstocks iso-pentane total content; The light hydrocarbon feedstocks that will remove then behind water and the iso-pentane carries out hydroisomerization reaction in the presence of solid super acid catalyst, described solid super acid catalyst comprises the zirconium dioxide of sulfur loaded acid group.
2. in accordance with the method for claim 1, it is characterized in that water-content is 5～15ppm in the described light hydrocarbon feedstocks that removes behind water and the iso-pentane.
3. in accordance with the method for claim 1, it is characterized in that removing that light hydrocarbon feedstocks behind water and the iso-pentane is 0.1～6.0 at 100～250 ℃, 0.5～3.0MPa, hydrogen/hydrocarbon molecule ratio, isomerization raw material volume space velocity 1.0～4.0 hours
-1Condition under carry out isomerization reaction.
4. in accordance with the method for claim 3, the temperature that it is characterized in that described isomerization reaction is that 130～200 ℃, pressure are that 1.5～2.0MPa, hydrogen/hydrocarbon molecule ratio are 1.5～3.0.
5. in accordance with the method for claim 1, it is characterized in that removing minor amount of water and iso-pentane in the light hydrocarbon feedstocks in rectifying tower, the rectifying tower tower top temperature is 65～75 ℃, and column bottom temperature is 115～125 ℃, and pressure tower is 0.45～0.55MPa.
6. in accordance with the method for claim 1, it is characterized in that also containing in the described solid super acid catalyst VIII family metal of 0.5～5.0 quality %, sulphur content is 0.5～5.0 quality % in the catalyzer.
7. in accordance with the method for claim 6, it is characterized in that described VIII family metal is a platinum.
8. in accordance with the method for claim 1, it is characterized in that the monocline phase content is 5～70 quality % in the described zirconium dioxide.
9. in accordance with the method for claim 1, it is characterized in that behind the hydroisomerization reaction hydrogen being separated with isomerization product, recycle, and the drying and dehydrating device is set on the recycle hydrogen pipeline.
10. in accordance with the method for claim 9, it is characterized in that filling A type molecular sieve or aluminum oxide in the described drying and dehydrating device, water-content is 1.0～10ppm in the circulating hydrogen of dehydration back.
11. in accordance with the method for claim 1, it is characterized in that described hysomer product after gas-liquid separation, the iso-pentane that product liquid and rectifying are removed mixes.
12. in accordance with the method for claim 1, it is characterized in that described light hydrocarbon feedstocks is C
5～C
6Lighter hydrocarbons, wherein normal paraffin content is 20～80 quality %.
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| CN101851530B (en) * | 2009-03-31 | 2013-04-24 | 中国石油化工股份有限公司 | Paraffin isomerization method of reducing benzene content |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1345913A (en) * | 2000-09-28 | 2002-04-24 | 中国石油化工股份有限公司 | Method for hydroisomerization of light hydrocarbon |
| CN1428196A (en) * | 2001-12-25 | 2003-07-09 | 中国石油化工股份有限公司 | Solid super acidic catalyst and its preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1345913A (en) * | 2000-09-28 | 2002-04-24 | 中国石油化工股份有限公司 | Method for hydroisomerization of light hydrocarbon |
| CN1428196A (en) * | 2001-12-25 | 2003-07-09 | 中国石油化工股份有限公司 | Solid super acidic catalyst and its preparation method |
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