CN102887809A - Method for hydroisomerizing normal alkane by using supported nickel phosphide catalyst - Google Patents
Method for hydroisomerizing normal alkane by using supported nickel phosphide catalyst Download PDFInfo
- Publication number
- CN102887809A CN102887809A CN2012103931913A CN201210393191A CN102887809A CN 102887809 A CN102887809 A CN 102887809A CN 2012103931913 A CN2012103931913 A CN 2012103931913A CN 201210393191 A CN201210393191 A CN 201210393191A CN 102887809 A CN102887809 A CN 102887809A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- nickel phosphide
- nickel
- supported nickel
- normal alkane
- 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.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for hydroisomerizing normal alkane by using a supported nickel phosphide catalyst, which comprises the following steps: loading the supported nickel phosphide catalyst in a fixed bed type reactor, feeding hydrogen gas and the normal alkane according to a mol ratio of (1-20):1, and performing isomerization reaction under the reaction conditions that the reaction temperature is 250-400 DEG C, the hydrogen gas pressure is 0.1-5.0 MPa and the weight hourly space velocity of the normal alkane is 0.1-10 h<-1>, wherein the supported nickel phosphide catalyst takes SAPO-11 as a carrier; the active phase is nickel phosphide; and the mass of nickel accounts for 0.5-10% of the mass of the catalyst. The supported nickel phosphide catalyst used in the invention has the advantages of high activity, good selectivity, low cost, no need of vulcanizing agent and the like, and has favorable application prospects.
Description
Technical field
The present invention relates to a kind of method with loading type catalyst of phosphatizing nickel normal paraffin hydroisomerization, belong to the hydrocarbon isomerization technical field.
Background technology
Along with the increasingly stringent that environmental regulation requires, people constantly increase the demand of clean gasoline, diesel oil and lubricated wet goods product.Hydroisomerization is a kind of important technology of production high-quality petroleum products.Utilize the hydroisomerization technology can improve gasoline octane rating, reduce condensation point or the pour point of diesel oil and lubricating oil, and have higher product yield.What hydroisomerization adopted is to have metallicity and acid dual-function catalyst.Wherein, metal component mainly comprises precious metal (such as Pt, Pd) or metallic sulfide (such as Ni-Co, Ni-W, Ni-Mo sulfides).The former is expensive can to affect its large-scale application, and the latter is only applicable to high sulfur-bearing raw material.In addition, nickel-base catalyst reduces product yield because having higher lytic activity.Therefore, the design and the preparation high-performance, the novel hydrogenation isomerization catalyst has important practical significance cheaply.
Summary of the invention
The present invention is intended to provide a kind of method with loading type catalyst of phosphatizing nickel normal paraffin hydroisomerization, and the catalyzer that the method adopts has the active high and good advantage of selectivity.
The present invention is realized that by following technical proposals a kind of method with loading type catalyst of phosphatizing nickel normal paraffin hydroisomerization is characterized in that comprising following process:
The loading type catalyst of phosphatizing nickel is housed in fixed-bed reactor, is 1 ~ 20:1 charging by hydrogen and normal paraffin mol ratio, at 250～400 ℃ of temperature of reaction, hydrogen pressure 0.1 ~ 5.0 MPa and normal paraffin weight hourly space velocity 0.1 ~ 10 h
-1Reaction conditions under carry out isomerization reaction; Described loading type catalyst of phosphatizing nickel is take the SAPO-11 molecular sieve as carrier, and its activity is nickel phosphide mutually, and wherein the quality of nickel accounts for 0.5～10% of catalyzer total mass; Described normal paraffin contains 6 ~ 18 carbon atoms.
The invention has the advantages that: the loading type catalyst of phosphatizing nickel that the method for normal alkane isomerization of the present invention adopts, compare with noble metal catalyst with metallic sulfide, that this catalyzer has is active high, selectivity is good, low-cost and need not to use the advantage such as vulcanizing agent, have a good application prospect.
Embodiment:
Embodiment 1. gets a certain amount of SAPO-11 molecular sieve carrier 110 ℃ of dryings 4 hours, adopts Ni (NO
3)
2And NH
4H
2PO
4Then mixing solutions (wherein the Ni/P ratio is 1) impregnated carrier 12 hours 110 ℃ of dryings 12 hours, prepared catalyst precursor in 4 hours 500 ℃ of roastings again in air atmosphere.These presoma 1.0 grams are placed quartz tube reactor, pass into the hydrogen that flow is 300 ml/min, elder generation is warming up to 250 ℃ with 5 ℃/minute speed by room temperature, then be warming up to 650 ℃ with 1 ℃/minute speed, and namely preparing the molecular sieve carried catalyst of phosphatizing nickel of SAPO-11 at 650 ℃ after keeping 3 hours, this catalyzer is at room temperature 0.5%O
2/ N
2Air-flow (100 ml/min) passivation is for subsequent use after 6 hours.Prepared catalyzer is the molecular sieve carried Ni of SAPO-11
2P, the mass content of nickel is 3% in this catalyzer.
Take n-dodecane as reactant, the Hydroisomerization Properties evaluation procedure of catalyzer is as follows: with the molecular sieve carried Ni of 1.0 gram SAPO-11 of passivation
2The P catalyzer fixed-bed reactor of packing into are in normal pressure and 450
oUse H under the C condition
2(100 ml/min) reduction 1 hour.After the reduction activation, temperature of reaction and hydrogen pressure are transferred to respectively 350
oC and 2.0 MPa, (the n-dodecane weight hourly space velocity is as 2 h to pass into hydrogen and n-dodecane take the speed of 4 l/hs and 2 Grams Per Hours respectively in the reactor
-1, H
2With the n-dodecane mol ratio be 15) carry out isomerization reaction, liquid product adopts gas-chromatography to analyze.Calculate by mass, the n-dodecane transformation efficiency is 90%, and the selectivity of Permethyl 99A. is 72%.
Embodiment 2. catalyst preparation process are with embodiment 1, and difference is the Ni (NO that adopts in the Kaolinite Preparation of Catalyst process
3)
2And NH
4H
2PO
4Hybrid infusion solution in the Ni/P ratio be 3, prepared catalyst is the molecular sieve carried Ni of SAPO-11
3P, the mass content of nickel is 3% in this catalyzer.The hygrogenating isomerization reaction condition of catalyzer is with embodiment 1.Calculate by mass, the n-dodecane transformation efficiency is 97%, and the selectivity of Permethyl 99A. is 61%.
Embodiment 3. catalyst preparation process are with embodiment 1, the Ni (NO that adopts when difference is Kaolinite Preparation of Catalyst
3)
2And NH
4H
2PO
4Mixing solutions in the Ni/P ratio be 0.5, prepared catalyzer is the molecular sieve carried Ni of SAPO-11
2P, the mass content of nickel is 3% in this catalyzer.The hygrogenating isomerization reaction condition of catalyzer is with embodiment 1.Calculate by mass, the n-dodecane transformation efficiency is 54%, and the selectivity of Permethyl 99A. is 62%.
Embodiment 4. catalyst preparation process are with embodiment 1, and difference is the prepared molecular sieve carried Ni of SAPO-11
2The mass content of Ni is 0.5% in the P catalyzer.The hygrogenating isomerization reaction condition of catalyzer is calculated by mass with embodiment 1, and the n-dodecane transformation efficiency is 95%, and the selectivity of Permethyl 99A. is 63%.
Embodiment 5. catalyst preparation process are with embodiment 1, and difference is the prepared molecular sieve carried Ni of SAPO-11
2The mass content of Ni is 10% in the P catalyzer.The hygrogenating isomerization reaction condition of catalyzer is calculated by mass with embodiment 1, and the n-dodecane transformation efficiency is 76%, and the selectivity of Permethyl 99A. is 68 %.
Embodiment 6. catalyst preparation process are with embodiment 1.The hygrogenating isomerization reaction condition of catalyzer is with embodiment 1, and difference is that reaction raw materials is normal hexane.Calculate by mass, the hexane conversion rate is 95%, and the selectivity of isohexane is 85%.
Embodiment 7. catalyst preparation process are with embodiment 1.The hygrogenating isomerization reaction condition of catalyzer is with embodiment 1, and difference is that reaction raw materials is Octadecane.Calculate by mass, the transformation efficiency of Octadecane is 88%, and the selectivity of isooctadecane is 75%.
Embodiment 8 ~ 15. adopts the prepared molecular sieve carried Ni of SAPO-11 of embodiment 1
2The P catalyzer take n-dodecane as reactant, adopts continuous fixed bed reactor, at differential responses temperature, pressure, n-dodecane weight hourly space velocity and H
2Investigated the reactivity worth of this catalyzer under the condition of/n-dodecane mol ratio, the result is as shown in table 1.
Ni under the table 1 differential responses condition
2The n-dodecane hygrogenating isomerization reaction performance of P/SAPO-11 catalyzer
| ? | Temperature of reaction ( oC) | H 2Pressure (MPa) | N-dodecane weight hourly space velocity (h -1） | H 2/ n-dodecane mol ratio | N-dodecane transformation efficiency (wt.%) | Permethyl 99A. selectivity (wt.%) |
| Embodiment 8 | 250 | 2 | 2 | 15 | 70 | 88 |
| Embodiment 9 | 400 | 2 | 2 | 15 | 99 | 70 |
| Embodiment 10 | 350 | 0.1 | 2 | 15 | 93 | 75 |
| Embodiment 11 | 350 | 5 | 2 | 15 | 82 | 73 |
| Embodiment 12 | 300 | 2 | 0.1 | 15 | 99 | 74 |
| Embodiment 13 | 350 | 2 | 10 | 15 | 75 | 76 |
| Embodiment 14 | 350 | 2 | 2 | 1 | 99 | 74 |
| Embodiment 15 | 350 | 2 | 2 | 20 | 80 | 75 |
Claims (1)
1. method with loading type catalyst of phosphatizing nickel normal paraffin hydroisomerization, it is characterized in that comprising following process: the loading type catalyst of phosphatizing nickel is housed in fixed-bed reactor, be 1 ~ 20:1 charging by hydrogen and normal paraffin mol ratio, at 250～400 ℃ of temperature of reaction, hydrogen pressure 0.1 ~ 5.0 MPa and normal paraffin weight hourly space velocity 0.1 ~ 10 h
-1Reaction conditions under carry out isomerization reaction; Described loading type catalyst of phosphatizing nickel is take the SAPO-11 molecular sieve as carrier, and its activity is nickel phosphide mutually, and wherein the quality of nickel accounts for 0.5～10% of catalyzer total mass; Described normal paraffin contains 6 ~ 18 carbon atoms.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012103931913A CN102887809A (en) | 2012-10-17 | 2012-10-17 | Method for hydroisomerizing normal alkane by using supported nickel phosphide catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012103931913A CN102887809A (en) | 2012-10-17 | 2012-10-17 | Method for hydroisomerizing normal alkane by using supported nickel phosphide catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102887809A true CN102887809A (en) | 2013-01-23 |
Family
ID=47531512
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012103931913A Pending CN102887809A (en) | 2012-10-17 | 2012-10-17 | Method for hydroisomerizing normal alkane by using supported nickel phosphide catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102887809A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103638968A (en) * | 2013-11-12 | 2014-03-19 | 中国石油大学(华东) | Preparation method and application method of non-noble metal reforming catalyst |
| CN103638954A (en) * | 2013-11-12 | 2014-03-19 | 中国石油大学(华东) | Preparation method and application method of non-noble metal dehydrogenation catalyst |
| CN104117382A (en) * | 2013-04-26 | 2014-10-29 | 中国石油天然气股份有限公司 | Hydrothermal preparation method of supported nickel phosphide catalyst |
| CN106748613A (en) * | 2017-01-19 | 2017-05-31 | 黑龙江大学 | A kind of method of hexadecane hygrogenating isomerization reaction on support type crystalline state catalyst of phosphatizing nickel |
| CN107376984A (en) * | 2017-06-19 | 2017-11-24 | 中国海洋石油总公司 | One kind is used for C10+The preparation method of the non-precious metal catalyst of heavy aromatics lighting |
| CN108212184A (en) * | 2016-12-22 | 2018-06-29 | 中国石油天然气股份有限公司 | Alkane isomerization catalyst and preparation method thereof |
| CN109569709A (en) * | 2018-11-12 | 2019-04-05 | 山东科技大学 | Load the Performance of Isomerization Catalysts for Light n-Paraffin and preparation method thereof of nickel sulfide |
| CN112090434A (en) * | 2020-09-16 | 2020-12-18 | 常州大学 | Preparation method of supported nickel phosphide for catalyzing selective hydrogenation of furfural to prepare furfuryl alcohol |
| CN113786857A (en) * | 2021-08-18 | 2021-12-14 | 中科博格(湖州)环保科技有限公司 | Biodiesel hydrodeoxygenation-isomerization catalyst and preparation method and application thereof |
| CN114956942A (en) * | 2022-06-01 | 2022-08-30 | 南京工业大学 | Process for catalyzing hydroisomerization of n-hexadecane |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001023501A1 (en) * | 1999-09-30 | 2001-04-05 | Virginia Tech Intellectual Properties, Inc. | Novel transition metal phosphide catalysts |
| CN101503201A (en) * | 2009-03-19 | 2009-08-12 | 中国石油大学(北京) | Preparations of SAPO-11 molecular sieve and SAPO-11 molecular sieve based catalyst |
-
2012
- 2012-10-17 CN CN2012103931913A patent/CN102887809A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001023501A1 (en) * | 1999-09-30 | 2001-04-05 | Virginia Tech Intellectual Properties, Inc. | Novel transition metal phosphide catalysts |
| CN101503201A (en) * | 2009-03-19 | 2009-08-12 | 中国石油大学(北京) | Preparations of SAPO-11 molecular sieve and SAPO-11 molecular sieve based catalyst |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104117382A (en) * | 2013-04-26 | 2014-10-29 | 中国石油天然气股份有限公司 | Hydrothermal preparation method of supported nickel phosphide catalyst |
| CN103638954A (en) * | 2013-11-12 | 2014-03-19 | 中国石油大学(华东) | Preparation method and application method of non-noble metal dehydrogenation catalyst |
| CN103638968B (en) * | 2013-11-12 | 2015-07-08 | 中国石油大学(华东) | Preparation method and application method of non-noble metal reforming catalyst |
| CN103638954B (en) * | 2013-11-12 | 2016-04-13 | 中国石油大学(华东) | A kind of preparation method of non-noble metal dehydrogenation catalyst and application process |
| CN103638968A (en) * | 2013-11-12 | 2014-03-19 | 中国石油大学(华东) | Preparation method and application method of non-noble metal reforming catalyst |
| CN108212184A (en) * | 2016-12-22 | 2018-06-29 | 中国石油天然气股份有限公司 | Alkane isomerization catalyst and preparation method thereof |
| CN106748613B (en) * | 2017-01-19 | 2019-10-22 | 黑龙江大学 | A kind of method of hexadecane hygrogenating isomerization reaction on support type crystalline state catalyst of phosphatizing nickel |
| CN106748613A (en) * | 2017-01-19 | 2017-05-31 | 黑龙江大学 | A kind of method of hexadecane hygrogenating isomerization reaction on support type crystalline state catalyst of phosphatizing nickel |
| CN107376984A (en) * | 2017-06-19 | 2017-11-24 | 中国海洋石油总公司 | One kind is used for C10+The preparation method of the non-precious metal catalyst of heavy aromatics lighting |
| CN109569709A (en) * | 2018-11-12 | 2019-04-05 | 山东科技大学 | Load the Performance of Isomerization Catalysts for Light n-Paraffin and preparation method thereof of nickel sulfide |
| CN112090434A (en) * | 2020-09-16 | 2020-12-18 | 常州大学 | Preparation method of supported nickel phosphide for catalyzing selective hydrogenation of furfural to prepare furfuryl alcohol |
| CN112090434B (en) * | 2020-09-16 | 2023-05-23 | 常州大学 | Preparation method of supported nickel phosphide for preparing furfuryl alcohol by catalyzing selective hydrogenation of furfural |
| CN113786857A (en) * | 2021-08-18 | 2021-12-14 | 中科博格(湖州)环保科技有限公司 | Biodiesel hydrodeoxygenation-isomerization catalyst and preparation method and application thereof |
| CN114956942A (en) * | 2022-06-01 | 2022-08-30 | 南京工业大学 | Process for catalyzing hydroisomerization of n-hexadecane |
| CN114956942B (en) * | 2022-06-01 | 2023-12-22 | 南京工业大学 | Process for catalyzing hydroisomerization of n-hexadecane |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102887809A (en) | Method for hydroisomerizing normal alkane by using supported nickel phosphide catalyst | |
| CN101927168B (en) | Nickel-based catalyst for preparing isopropyl alcohol by acetone hydrogenation and application thereof | |
| CN102688768B (en) | Cobalt-based catalyst for synthesizing ethanol, preparation method and application thereof | |
| CN104226354B (en) | A kind of catalyzer for acetone hydrogenation preparing isopropanol and method for making and application | |
| CN104119943A (en) | Method for preparing aviation kerosene from furyl oxygen-containing organic compounds by hydrogenation deoxidation | |
| CN104711012A (en) | Applications of hydrodeoxygenation catalyst in synthesis of renewable diesel fuel or aviation kerosene | |
| CN102836737B (en) | Naphthalene hydrogenation catalyst and preparation method thereof | |
| CN110152663A (en) | It is a kind of for the catalyst of preparation by furfural gas phase hydrogenation furfuryl alcohol and its preparation and application | |
| CN102585876A (en) | Method for preparing hydrocarbon from higher aliphatic ester by metal phosphide catalyst | |
| CN113578352A (en) | High-stability fixed bed hydrodeoxygenation catalyst and preparation method and application thereof | |
| CN102908957B (en) | Method for Fischer-Tropsch synthesis | |
| CN111054346B (en) | Catalyst for preparing high-carbon olefin from synthesis gas and preparation method and application thereof | |
| CN101474568B (en) | Selective hydrogenation olefin-removing bimetallic phosphide catalyst and preparation method thereof | |
| CN102166519A (en) | Method for preparing loaded amorphous nickel-based catalyst | |
| CN103772207A (en) | Method for preparing cyclohexylamine with high selectivity from nitrobenzene in one-step catalytic hydrogenation mode | |
| WO2016180000A1 (en) | Two-step ethylene glycol and 1,2-propylene glycol preparation method using cellulose | |
| CN103539676A (en) | Method for preparing m-xylylenediamine from m-phthalodinitrile through hydrogenation | |
| CN102911693B (en) | Fischer-Tropsch synthesis method by employing mixed catalyst | |
| CN102417161B (en) | Method for producing CO-free hydrogen by steam reformation based on biomass alcohol as raw material | |
| CN107488457B (en) | A kind of biomass liquid fuel and the preparation method and application thereof | |
| CN102309991B (en) | Preparation method for cobalt-based Fischer-Tropsch synthesis catalyst | |
| CN102911695B (en) | Fischer-Tropsch synthetic method of mixed system by using different catalysts | |
| CN105562019A (en) | Mercaptan thioetherfication catalyst | |
| CN102838439B (en) | Method for producing decahydronaphthalene through naphthalene hydrogenation | |
| CN1916121B (en) | Method for preparing diene selective hydrotreating catalyst for gasoline |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20130123 |