CN105289714B - A kind of composite catalyst for gasoline hydrogenation - Google Patents
A kind of composite catalyst for gasoline hydrogenation Download PDFInfo
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- CN105289714B CN105289714B CN201510927503.8A CN201510927503A CN105289714B CN 105289714 B CN105289714 B CN 105289714B CN 201510927503 A CN201510927503 A CN 201510927503A CN 105289714 B CN105289714 B CN 105289714B
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- composite catalyst
- carrier
- molecular sieve
- dipped
- aluminium chloride
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- 239000003054 catalyst Substances 0.000 title claims abstract description 29
- 239000003502 gasoline Substances 0.000 title claims abstract description 18
- 239000002131 composite material Substances 0.000 title claims abstract description 16
- 238000005984 hydrogenation reaction Methods 0.000 title abstract description 13
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 20
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 15
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 15
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002808 molecular sieve Substances 0.000 claims abstract description 14
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000002803 maceration Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims abstract description 8
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims abstract description 7
- 229940010552 ammonium molybdate Drugs 0.000 claims abstract description 7
- 235000018660 ammonium molybdate Nutrition 0.000 claims abstract description 7
- 239000011609 ammonium molybdate Substances 0.000 claims abstract description 7
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000005245 sintering Methods 0.000 claims abstract description 7
- 235000019795 sodium metasilicate Nutrition 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000001354 calcination Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 7
- 239000011148 porous material Substances 0.000 abstract description 6
- 238000006477 desulfuration reaction Methods 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 238000004523 catalytic cracking Methods 0.000 description 9
- 150000001336 alkenes Chemical class 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 241000772415 Neovison vison Species 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of composite catalyst for gasoline hydrogenation, its step is as follows：1）It is prepared by carrier：Liquor alumini chloridi and sodium silicate solution is respectively configured in a certain amount of aluminium chloride and sodium metasilicate；Molecular sieve is dipped in liquor alumini chloridi, dried naturally after taking-up, then molecular sieve is dipped in sodium silicate solution, is dried naturally；Molecular sieve after drying is calcined under certain sintering temperature can obtain plated film molecular sieve carrier；2）The preparation of catalyst：Using the mixed solution of ferric nitrate, nickel nitrate and ammonium molybdate as maceration extract, maceration extract 2min, 120 DEG C of dry 30min are immersed in through carrier at room temperature；Repeat 25 times, be 500 DEG C of calcinations 4 hours, composite catalyst is can obtain after natural cooling.The present invention has suitable pore size distribution$ and active metal, the characteristics of with stable in physicochemical property, high-specific surface area, pore volume and higher desulfuration selectivity, and raw material is easy to get, process simply.
Description
Technical field
The invention belongs to gasoline processing technique field, and in particular to a kind of composite catalyst for gasoline hydrogenation.
Background technology
Be hydrocracked, be in the technique in a kind of petrochemical industry, i.e. petroleum refining process under higher pressure and temperature,
Hydrogen makes mink cell focus occur hydrogenation, cracking and isomerization reaction through catalyst action, is converted into light oil（Gasoline, kerosene, diesel oil
Or catalytic cracking, the raw material of cracking alkene processed）Process.It is carrying out catalytic cracking reaction from unlike catalytic cracking
When, while with hydrocarbons hydrogenation reaction.The combination of substantially hydrogenation and catalytic cracking process is hydrocracked, can be made
Heavy oil product generates the light-end products such as gasoline, kerosene and diesel oil by catalytic cracking reaction, can prevent from generating substantial amounts of Jiao again
Charcoal, can also be by impurity removals such as the sulphur in raw material, nitrogen, oxygen, and makes alkene saturation.Be hydrocracked with yield of light oil it is high,
The outstanding feature of good product quality.Plus gasoline generally need to could turn into high-knock rating gasoline through catalytic reforming again.But equipment investment
It is high with processing charges, using not as catalytic cracking, extensively, the latter is usually used in the impurity such as processing sulfur-bearing and containing the more raw material of aromatic hydrocarbons,
Such as catalytic cracking heavy distillate or shale oil.
1930s, Germany and Britain handle coal by the use of tungsten disulfide-Emathlite as hydrocracking catalyst
Tar.50~sixties, the U.S. uses the catalyst of greater activity, the application being hydrocracked progressively is promoted, and build up
Fixed bed hydrogenation cracking and fluidized-bed hydrogenation cracking unit (see fixed bed reactors, fluidized-bed reactor).The former is in industry
Wide application is obtained in production, many patented technologies are occurred in that;The latter is expensive because of equipment, and commercial plant is less.1966
Year, Chinese independently developed year disposal ability 300kt hydrocracking units put into production in Daqing Refinery.
The liquid product yield being hydrocracked is up to more than 98%, and its quality is also high far beyond catalytic cracking.Although being hydrocracked
Many advantages, but because it is to operate under high pressure, condition is harsher, need more alloy steel products, and consumption hydrogen is more, investment compared with
Height, therefore without commonly used as catalytic cracking.
The content of the invention
It is an object of the invention to provide a kind of composite catalyst for gasoline hydrogenation, with suitable pore size distribution$ and
Active metal, the characteristics of with stable in physicochemical property, high-specific surface area, pore volume and higher desulfuration selectivity, and raw material is easy
Obtain, process simple.
A kind of composite catalyst for gasoline hydrogenation, including activating oxide and carrier, its step are as follows：
1）It is prepared by carrier：Liquor alumini chloridi and sodium silicate solution is respectively configured in a certain amount of aluminium chloride and sodium metasilicate；Will
Molecular sieve is dipped in liquor alumini chloridi, is dried naturally after taking-up, and then molecular sieve is dipped in sodium silicate solution, is dried in the air naturally
It is dry；Molecular sieve after drying is calcined under certain sintering temperature；The natural cooling after above-mentioned immersion-roasting for several times, you can obtain
Plated film molecular sieve carrier；
2）The preparation of catalyst：Using the mixed solution of ferric nitrate, nickel nitrate and ammonium molybdate as maceration extract, at room temperature through carrying
Body is immersed in maceration extract 2min, 120 DEG C of dry 30min；Repeat 2-5 times, be 500 DEG C of calcinations 4 hours, natural cooling it
It can obtain composite catalyst afterwards.
Wherein, the step 1）In the particle diameter of aluminium chloride powder be not more than 10 microns.
Wherein, the step 1）In aluminium chloride and sodium metasilicate proportioning be 3:1.
Wherein, the step 1）Sintering temperature be 500-600 DEG C.
Wherein, the step 2）Ferric nitrate, the proportioning of nickel nitrate and ammonium molybdate be 1:6:4.
Compared with prior art, the invention has the advantages that：The present invention has suitable pore size distribution$ and work
Property metal, the characteristics of with stable in physicochemical property, high-specific surface area, pore volume and higher desulfuration selectivity, and raw material be easy to get,
Processing is simple.
Embodiment
The present invention is described further with reference to embodiment：
Embodiment 1
A kind of composite catalyst for gasoline hydrogenation, including activating oxide and carrier, its step are as follows：
1）It is prepared by carrier：Liquor alumini chloridi and sodium silicate solution is respectively configured in a certain amount of aluminium chloride and sodium metasilicate；Will
Molecular sieve is dipped in liquor alumini chloridi, is dried naturally after taking-up, and then molecular sieve is dipped in sodium silicate solution, is dried in the air naturally
It is dry；Molecular sieve after drying is calcined under certain sintering temperature；The natural cooling after above-mentioned immersion-roasting for several times, you can obtain
Plated film molecular sieve carrier；
2）The preparation of catalyst：Using the mixed solution of ferric nitrate, nickel nitrate and ammonium molybdate as maceration extract, at room temperature through carrying
Body is immersed in maceration extract 2min, 120 DEG C of dry 30min；Repeat 2-5 times, be 500 DEG C of calcinations 4 hours, natural cooling it
It can obtain composite catalyst afterwards.
Wherein, the step 1）In the particle diameter of aluminium chloride powder be not more than 10 microns.
Wherein, the step 1）In aluminium chloride and sodium metasilicate proportioning be 3:1.
Wherein, the step 1）Sintering temperature be 500-600 DEG C.
Wherein, the step 2）Ferric nitrate, the proportioning of nickel nitrate and ammonium molybdate be 1:6:4.
Etherificate experiment：
Using Jinxi refinery heavy oil catalytically cracked gasoline as raw material, the hydrodesulfurization performance and olefin saturation performance of catalyst are carried out
It can evaluate.Catalytic reaction temperature is 280 DEG C, reaction pressure 3.0MPa, liquid hourly space velocity (LHSV) 2h-1, hydrogen-oil ratio 600（Volume ratio）Under
Hydrodesulfurization and olefin saturation performance can result it is as follows.
| Analysis project | Blank | Plus aluminium oxide catalyst | Catalyst of the present invention |
| Alkane mass fraction/% | 9.8 | 28.4 | 41.6 |
| Olefin content/% | 55.3 | 40.1 | 18.2 |
| Aromatics quality fraction/% | 35.9 | 31.5 | 40.2 |
| Sulfur nutrient/% | 57.2 | 37.0 | 29.2 |
| Octane number | 92.7 | 88.6 | 92.3 |
| Octane number reduced rate/% | 4.1 | 0.4 |
Found through application example, catalyst of the present invention has preferable hydrodesulfurization selectivity.With conventional Al2O3Catalysis
Agent is compared, and catalyst of the present invention restrains absorption and the hydrogenation saturated reaction of alkene, improves desulfurization of the catalyst to gasoline and selects
Property.
One embodiment of the invention is the foregoing is only, the present invention, all use equivalent substitutions or equivalent transformation is not intended to limit
The technical scheme that is obtained of mode, all fall within protection scope of the present invention.
Claims (4)
1. a kind of application of composite catalyst in gasoline hydrodesulfurizationmethod, it is characterised in that：The composite catalyst includes activity
Oxide and carrier, its step are as follows：
1）It is prepared by carrier：Liquor alumini chloridi and sodium silicate solution is respectively configured in a certain amount of aluminium chloride and sodium metasilicate；By molecule
Sieve is dipped in liquor alumini chloridi, is dried, then molecular sieve is dipped in sodium silicate solution naturally after taking-up, is dried naturally；
Molecular sieve after drying is calcined under certain sintering temperature；The natural cooling after above-mentioned immersion-roasting for several times, you can plated
Membrane molecule sieves carrier；
2）The preparation of catalyst：Using the mixed solution of ferric nitrate, nickel nitrate and ammonium molybdate as maceration extract, soaked at room temperature through carrier
Bubble is in maceration extract 2min, 120 DEG C of dry 30min；Repeat 2-5 times, be 500 DEG C of calcinations 4 hours, it is naturally cold
But composite catalyst is can obtain after；
The step 1）In the particle diameter of aluminium chloride powder be not more than 10 microns.
2. application of the composite catalyst according to claims 1 in gasoline hydrodesulfurizationmethod, it is characterised in that described
Step 1）In aluminium chloride and sodium metasilicate proportioning be 3:1.
3. application of the composite catalyst according to claims 1 in gasoline hydrodesulfurizationmethod, it is characterised in that described
Step 1）Sintering temperature be 500-600 DEG C.
4. application of the composite catalyst according to claims 1 in gasoline hydrodesulfurizationmethod, it is characterised in that described
Step 2）Ferric nitrate, the proportioning of nickel nitrate and ammonium molybdate be 1:6:4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510927503.8A CN105289714B (en) | 2015-12-14 | 2015-12-14 | A kind of composite catalyst for gasoline hydrogenation |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510927503.8A CN105289714B (en) | 2015-12-14 | 2015-12-14 | A kind of composite catalyst for gasoline hydrogenation |
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| Publication Number | Publication Date |
|---|---|
| CN105289714A CN105289714A (en) | 2016-02-03 |
| CN105289714B true CN105289714B (en) | 2017-11-07 |
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| CN201510927503.8A Active CN105289714B (en) | 2015-12-14 | 2015-12-14 | A kind of composite catalyst for gasoline hydrogenation |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030221993A1 (en) * | 2002-05-30 | 2003-12-04 | Kaminsky Mark P. | Pyrolysis gasoline stabilization |
| CN1951568A (en) * | 2005-10-19 | 2007-04-25 | 中国石油化工股份有限公司 | A method for preparing supported catalyst |
| CN103801359A (en) * | 2014-02-13 | 2014-05-21 | 武汉科林精细化工有限公司 | Hydro-upgrading catalyst for byproduct heavy petrol of methanol to gasoline (MTG), and preparation method thereof |
-
2015
- 2015-12-14 CN CN201510927503.8A patent/CN105289714B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030221993A1 (en) * | 2002-05-30 | 2003-12-04 | Kaminsky Mark P. | Pyrolysis gasoline stabilization |
| CN1951568A (en) * | 2005-10-19 | 2007-04-25 | 中国石油化工股份有限公司 | A method for preparing supported catalyst |
| CN103801359A (en) * | 2014-02-13 | 2014-05-21 | 武汉科林精细化工有限公司 | Hydro-upgrading catalyst for byproduct heavy petrol of methanol to gasoline (MTG), and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN105289714A (en) | 2016-02-03 |
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