CN105289714A - Composite catalyst for gasoline hydrogenation - Google Patents
Composite catalyst for gasoline hydrogenation Download PDFInfo
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- CN105289714A CN105289714A CN201510927503.8A CN201510927503A CN105289714A CN 105289714 A CN105289714 A CN 105289714A CN 201510927503 A CN201510927503 A CN 201510927503A CN 105289714 A CN105289714 A CN 105289714A
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- CN
- China
- Prior art keywords
- molecular sieve
- composite catalyst
- carrier
- catalyst
- gasoline hydrogenation
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- 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.)
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- 239000003054 catalyst Substances 0.000 title claims abstract description 31
- 239000003502 gasoline Substances 0.000 title claims abstract description 19
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 17
- 239000002131 composite material Substances 0.000 title claims abstract description 16
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 24
- 239000002808 molecular sieve Substances 0.000 claims abstract description 17
- 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 17
- 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
- 239000000243 solution Substances 0.000 claims abstract description 10
- 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
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 238000001816 cooling 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
- 238000002803 maceration Methods 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 6
- 230000003213 activating effect Effects 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 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
- 239000007788 liquid Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 238000002791 soaking Methods 0.000 abstract 3
- 238000005470 impregnation Methods 0.000 abstract 2
- 229940115440 aluminum sodium silicate Drugs 0.000 abstract 1
- 230000023556 desulfurization Effects 0.000 abstract 1
- 238000010304 firing Methods 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- 238000004523 catalytic cracking Methods 0.000 description 9
- 238000004517 catalytic hydrocracking Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 6
- 238000005336 cracking Methods 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 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
- 238000006243 chemical 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
- 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
- 239000002199 base oil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 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
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a composite catalyst for gasoline hydrogenation. The preparation method comprises the following steps: (1) preparing a carrier, namely respectively preparing an aluminum chloride solution and a sodium silicate solution by using a certain amount of aluminum chloride and sodium silicate, soaking a molecular sieve in the aluminum chloride solution, taking out the molecular sieve, naturally airing, soaking the molecular sieve in the sodium silicate solution, naturally airing, and calcining the aired molecular sieve at a certain calcination temperature, thereby obtaining a coated molecular sieve carrier; and (2) preparing a catalyst, namely by taking a mixed solution of ferric nitrate, nickel nitrate and ammonium molybdate as impregnation liquid, soaking the carrier in the impregnation liquid for 2 minutes at room temperature, drying at the temperature of 120 DEG C for 30 minutes, repeating the operation for 2-5 times, firing at the temperature of 500 DEG C for 4 hours, and naturally cooling, thereby obtaining the composite catalyst. The catalyst disclosed by the invention has proper pore structure distribution and reactive metals and has the characteristics of stable physicochemical properties, high specific surface area, high pore volume and high desulfurization selectivity; and moreover, the raw materials are readily available, and the processing operation is simple.
Description
Technical field
The invention belongs to gasoline processing technique field, be specifically related to a kind of composite catalyst for gasoline hydrogenation.
Background technology
Hydrocracking, the technique in a kind of petrochemical industry, namely in petroleum refining process under higher pressure and temperature, hydrogen makes mink cell focus generation hydrogenation, cracking and isomerization reaction through catalyst action, is converted into the process of light oil (raw material of gasoline, kerosene, diesel oil or catalytic cracking, cracking alkene).It and catalytic cracking, unlike carrying out Catalytic Cracking Unit of Measure at once, are attended by hydrocarbons hydrogenation reaction simultaneously.Hydrocracking is in fact the combination of hydrogenation and catalytic cracking process, heavy oil product can be made to generate the light-end products such as gasoline, kerosene and diesel oil by catalytic cracking reaction, can prevent from again generating a large amount of coke, by impurity removals such as the sulphur in raw material, nitrogen, oxygen, and olefin saturated can also be made.Hydrocracking has that yield of light oil is high, the outstanding feature of good product quality.Add gasoline usually to need just can become high-knock rating gasoline through catalytic reforming again.But equipment investment and processing charges high, application is extensive not as catalytic cracking, and the latter is usually used in processing the impurity such as sulfur-bearing and containing the more raw material of aromatic hydrocarbons, as catalytic cracking heavy distillate or shale wet goods.
The thirties in 20th century, Germany and Britain utilize tungsten disulfide-Emathlite as hydrocracking catalyst process coal tar.50 ~ sixties, the U.S. adopts the catalyst of greater activity, the application of hydrocracking is progressively promoted, and has built up fixed bed hydrogenation cracking and fluidized-bed hydrogenation cracking unit (see fixed bed reactors, fluidized-bed reactor).The former obtains applying more widely in the industrial production, has occurred many patented technologies; The latter is because of apparatus expensive, and commercial plant is less.1966, Chinese independently developed year disposal ability 300kt hydrocracking unit put into production at Daqing Refinery.
The liquid product yield of hydrocracking reaches more than 98%, and its quality is also high far beyond catalytic cracking.Although hydrocracking has many advantages, because it under high pressure operates, condition is harsher, needs more alloy steel products, and consumption hydrogen is more, invests higher, therefore does not generally apply as catalytic cracking.
Summary of the invention
The object of this invention is to provide a kind of composite catalyst for gasoline hydrogenation, there is suitable pore size distribution$ and active metal, there is the feature of stable in physicochemical property, high-specific surface area, pore volume and higher desulfuration selectivity, and raw material is easy to get, processes simply.
For a composite catalyst for gasoline hydrogenation, comprise activating oxide and carrier, its step is as follows:
1) carrier preparation: a certain amount of aluminium chloride and sodium metasilicate are configured liquor alumini chloridi and sodium silicate solution respectively; Molecular sieve is dipped in liquor alumini chloridi, naturally dries after taking out, then molecular sieve is dipped in sodium silicate solution, naturally dries; The roasting under certain sintering temperature of molecular sieve after drying; Naturally cool after above-mentioned immersion-roasting for several times, plated film molecular sieve carrier can be obtained;
2) preparation of catalyst: with the mixed solution of ferric nitrate, nickel nitrate and ammonium molybdate for maceration extract, is at room temperature immersed in maceration extract 2min through carrier, 120 DEG C of dry 30min; Repeat 2-5 time, be 500 DEG C of calcinations 4 hours, naturally can obtain composite catalyst after cooling.
Wherein, the particle diameter of the aluminium chloride powder in described step 1) is not more than 10 microns.
Wherein, the aluminium chloride in described step 1) and the proportioning of sodium metasilicate are 3:1.
Wherein, the sintering temperature of described step 1) is 500-600 DEG C.
Wherein, described step 2) the proportioning of ferric nitrate, nickel nitrate and ammonium molybdate be 1:6:4.
Compared with prior art, the present invention has following beneficial effect: the present invention has suitable pore size distribution$ and active metal, has the feature of stable in physicochemical property, high-specific surface area, pore volume and higher desulfuration selectivity, and raw material is easy to get, processes simply.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further:
Embodiment 1
For a composite catalyst for gasoline hydrogenation, comprise activating oxide and carrier, its step is as follows:
1) carrier preparation: a certain amount of aluminium chloride and sodium metasilicate are configured liquor alumini chloridi and sodium silicate solution respectively; Molecular sieve is dipped in liquor alumini chloridi, naturally dries after taking out, then molecular sieve is dipped in sodium silicate solution, naturally dries; The roasting under certain sintering temperature of molecular sieve after drying; Naturally cool after above-mentioned immersion-roasting for several times, plated film molecular sieve carrier can be obtained;
2) preparation of catalyst: with the mixed solution of ferric nitrate, nickel nitrate and ammonium molybdate for maceration extract, is at room temperature immersed in maceration extract 2min through carrier, 120 DEG C of dry 30min; Repeat 2-5 time, be 500 DEG C of calcinations 4 hours, naturally can obtain composite catalyst after cooling.
Wherein, the particle diameter of the aluminium chloride powder in described step 1) is not more than 10 microns.
Wherein, the aluminium chloride in described step 1) and the proportioning of sodium metasilicate are 3:1.
Wherein, the sintering temperature of described step 1) is 500-600 DEG C.
Wherein, described step 2) the proportioning of ferric nitrate, nickel nitrate and ammonium molybdate be 1:6:4.
Etherificate is tested:
With Jinxi refinery heavy oil catalytically cracked gasoline for raw material, carry out hydrodesulfurization performance and the evaluation of olefin saturated performance of catalyst.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 saturated performance result as follows.
| Analysis project | Blank | Add 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 mark/% | 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 |
Find through application example, it is selective that catalyst of the present invention has good hydrodesulfurization.With the Al of routine
2o
3catalyst is compared, and absorption and the hydrotreated lube base oil of catalyst supression alkene of the present invention react, and improve the desulfuration selectivity of catalyst to gasoline.
The foregoing is only one embodiment of the invention, do not limit the present invention, the technical scheme that the mode that all employings are equal to replacement or equivalent transformation obtains, all drop in protection scope of the present invention.
Claims (5)
1. for a composite catalyst for gasoline hydrogenation, it is characterized in that: it comprises activating oxide and carrier, its step is as follows:
1) carrier preparation: a certain amount of aluminium chloride and sodium metasilicate are configured liquor alumini chloridi and sodium silicate solution respectively; Molecular sieve is dipped in liquor alumini chloridi, naturally dries after taking out, then molecular sieve is dipped in sodium silicate solution, naturally dries; The roasting under certain sintering temperature of molecular sieve after drying; Naturally cool after above-mentioned immersion-roasting for several times, plated film molecular sieve carrier can be obtained;
2) preparation of catalyst: with the mixed solution of ferric nitrate, nickel nitrate and ammonium molybdate for maceration extract, is at room temperature immersed in maceration extract 2min through carrier, 120 DEG C of dry 30min; Repeat 2-5 time, be 500 DEG C of calcinations 4 hours, naturally can obtain composite catalyst after cooling.
2. a kind of composite catalyst for gasoline hydrogenation according to claims 1, is characterized in that, the particle diameter of the aluminium chloride powder in described step 1) is not more than 10 microns.
3. a kind of composite catalyst for gasoline hydrogenation according to claims 1, is characterized in that, the aluminium chloride in described step 1) and the proportioning of sodium metasilicate are 3:1.
4. a kind of composite catalyst for gasoline hydrogenation according to claims 1, is characterized in that, the sintering temperature of described step 1) is 500-600 DEG C.
5. a kind of composite catalyst for gasoline hydrogenation according to claims 1, is characterized in that, described step 2) the proportioning of ferric nitrate, 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 |
Applications Claiming Priority (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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| Publication Number | Publication Date |
|---|---|
| CN105289714A true CN105289714A (en) | 2016-02-03 |
| CN105289714B 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 |
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| CN105289714B (en) | 2017-11-07 |
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