CN104263400B - A kind of technique of methanol conversion - Google Patents

A kind of technique of methanol conversion Download PDF

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Publication number
CN104263400B
CN104263400B CN201410416433.5A CN201410416433A CN104263400B CN 104263400 B CN104263400 B CN 104263400B CN 201410416433 A CN201410416433 A CN 201410416433A CN 104263400 B CN104263400 B CN 104263400B
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CN
China
Prior art keywords
technique
methanol conversion
catalyst
methanol
diesel oil
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Expired - Fee Related
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CN201410416433.5A
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Chinese (zh)
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CN104263400A (en
Inventor
赵锦玲
王宏铭
王安桥
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WUHU NIUTAI INTELLECTURAL PROPERTY INFORMATION CONSULTANT CO., LTD
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芜湖市纽泰知识产权信息咨询有限公司
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Priority to CN201410416433.5A priority Critical patent/CN104263400B/en
Publication of CN104263400A publication Critical patent/CN104263400A/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/54—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The object of the present invention is to provide a kind of technique of methanol conversion, can be the high-quality diesel oil being rich in straight chain hydrocarbon by methanol conversion.In this technique, mixed packing carbinol resolving catalyst and fischer-tropsch synthetic catalyst in same reactor, after material benzenemethanol enters reactor, catalyzed dose is decomposed into synthetic gas, and the building-up process of continuing appropriation holder simultaneously changes diesel oil into.Utilize the present invention, in the relatively oversaturated situation in ammonia from coal market, the methanol conversion of a part can be become diesel oil fuel, realize the efficiency utilization to existing resource.

Description

A kind of technique of methanol conversion
Technical field
The present invention relates to a kind of technique of methanol conversion, being specifically related to a kind of is the processing method of the high-quality diesel oil being rich in straight chain hydrocarbon by methanol conversion.
Background technology
Methyl alcohol is a kind of widely used basic chemical raw materials.Senior alcohols can be prepared from methyl alcohol, ester compound, more derivative can be synthesized with other industrial chemicals such as benzene, and methyl alcohol also can be converted into Fuel Petroleum.The MTG technology of Mobile company is exactly the technique of typical preparing gasoline by methanol.In MTG technique, the ZSM-5 molecular sieve of the various modification of main employing, with the conversion of two sections, fixed bed, first paragraph is dimethyl ether by methanol dehydration, generates gasoline from the mixture of first paragraph methyl alcohol, dme and water out second segment reactor with ZSM-5 contact action.Be diesel oil by methanol conversion, that will make the application surface of the technique from methyl alcohol in Coal Chemical Industry more widen.
Summary of the invention
The object of the present invention is to provide a kind of technique of methanol conversion.In this technique, be first synthetic gas by the cartalytic decomposition effect of methyl alcohol by methanol conversion, the namely gas mixture of CO and H2, then produces synthetic gas the diesel component being rich in straight chain hydrocarbon again in same reactor by Fischer-Tropsch synthesis.The feature of this technique is, methanol oxidation decomposition course and Fischer-Tropsch synthesis carry out in same fixed-bed reactor, and catalyst in reactor bed is single hop, and the catalyzer loaded is two kinds, a kind of is the carbinol resolving catalyst of Cu system, another kind is the fischer-tropsch synthetic catalyst of Co system, is jointly filled in beds after two kinds of catalyst mix.
Methanolysis is the reaction of synthetic gas is a reaction of absorbing heat, and Cu-series catalyst carries out, such as Cu-Zn-Al system.Consider from thermodynamics, favors low temperature carries out in methyl alcohol to the direction being decomposed into synthetic gas, but consider from kinetics, in order to make reaction process effectively carry out, in actual industrial process, methyl alcohol is decomposed into the temperature of reaction of synthetic gas between 200 DEG C to 280 DEG C under catalyst action.
The process of a heat release through the process that F-T synthesis produces diesel component by synthetic gas, how to carry out on Co series catalysts, consider from raising diesel component selectivity angle, cryogenic high pressure is conducive to F-T synthesis and produces diesel oil, so in actual production operating process, F-T synthesis is also between 200 DEG C to 250 DEG C.The effect tendency of reaction pressure to methanolysis and F-T synthesis two processes is also consistent, higher pressure is all favourable to the two, therefore, the catalyzer that these two processes use can be placed in same reactor, and mix these two kinds of catalyzer together, make use of the heat coupling between methanol decomposition process and Fischer-Tropsch synthesis just, the feature that Process of absorption or liberation of heat process is mutually promoted, improves the equilibrium conversion that overall methyl alcohol transforms to diesel oil.
Methanol conversion can be the high-quality diesel oil being rich in straight chain hydrocarbon by the technique of a kind of methanol conversion provided by the invention.This technique comprises following several unit: turnover material-heat-exchanging unit E101, heating raw materials unit E102, reaction member R001, cooling unit E103, gas-liquid separation unit EF104.
Methanol conversion is the high-quality diesel oil being rich in straight chain hydrocarbon by the technique of a kind of methanol conversion provided by the invention.Technical process as shown in Figure 1, the methanol feedstock of liquid passes in and out material-heat-exchanging unit through E101() time, by from R001(reaction member) in the product heats that flows out, and then through E102(heating raw materials unit) be heated to temperature of reaction after enter R001(reaction member), after agent bed, flow out from R001, material-heat-exchanging unit is passed in and out through E101() time, after methanol feeding logistics cooling, again by E103(cooling unit) continue cooling after, enter EF104(gas-liquid separation unit), gas-liquid two-phase product enters downstream units after realizing separation.
Utilize the technique of a kind of methanol conversion provided by the invention, can be the high-quality diesel oil being rich in straight chain hydrocarbon by methanol conversion, in the relatively oversaturated situation in ammonia from coal market, the methanol conversion of a part can be become diesel oil fuel, not only efficiently utilize existing resource, but also provide fuel oil source of high quality and at a reasonable price to national society.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet (dotted line is heat transferring medium) of a kind of methanol conversion process provided by the invention.
Embodiment
Below in conjunction with drawings and Examples, the present invention is further detailed.
The following examples only for explaining explanation the present invention in detail, and limit the scope of the invention never in any form.
Embodiment 1
Methanol feeding enters R001 after the heating of E101 and E102, wherein in beds mixed packing be the methanol cracking catalyst of Cu-Zn-Al system and the fischer-tropsch synthetic catalyst of Co system, beds temperature is topmost 270 DEG C.The product flowed out from R001 reactor, after the cooling of E101 and E103, is divided into gas-liquid two-phase in EF104, flows into downstream units respectively.

Claims (3)

1. the technique of a methanol conversion, the flow process realizing this technique comprises, turnover material-heat-exchanging unit (E101), heating raw materials unit (E102), reaction member (R001), cooling unit (E103), gas-liquid separation unit (EF104), it is characterized in that mixed packing carbinol resolving catalyst and fischer-tropsch synthetic catalyst in reaction member (R001), utilize carbinol resolving catalyst to decompose the synthetic gas obtained, obtain diesel component by F-T synthesis.
2. the technique of a kind of methanol conversion according to claim 1, it is characterized in that in turnover material-heat-exchanging unit (E101), cold medium is liquid methanol feedstock, thermal medium is the product flowed out from reaction member (R001).
3. the technique of a kind of methanol conversion according to claim 1, it is characterized in that reaction member (R001) is single hop fixed-bed reactor, the temperature of whole beds upper end is 200 DEG C-275 DEG C.
CN201410416433.5A 2014-08-22 2014-08-22 A kind of technique of methanol conversion Expired - Fee Related CN104263400B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410416433.5A CN104263400B (en) 2014-08-22 2014-08-22 A kind of technique of methanol conversion

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Application Number Priority Date Filing Date Title
CN201410416433.5A CN104263400B (en) 2014-08-22 2014-08-22 A kind of technique of methanol conversion

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CN104263400A CN104263400A (en) 2015-01-07
CN104263400B true CN104263400B (en) 2016-01-20

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1417291A (en) * 2001-11-05 2003-05-14 中国科学院大连化学物理研究所 Technological process of preparing diesel oil fraction selectively with Fischer-tropsch synthetic gas

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8137531B2 (en) * 2003-11-05 2012-03-20 Chevron U.S.A. Inc. Integrated process for the production of lubricating base oils and liquid fuels from Fischer-Tropsch materials using split feed hydroprocessing

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1417291A (en) * 2001-11-05 2003-05-14 中国科学院大连化学物理研究所 Technological process of preparing diesel oil fraction selectively with Fischer-tropsch synthetic gas

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
费托合成CeO2助Co/SiO2催化剂的失活;代小平等;《催化学报》;20071231;第1047页-第1050页 *

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