CN101597520A - A kind of hydrocarbon hydro-conversion method - Google Patents
A kind of hydrocarbon hydro-conversion method Download PDFInfo
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- CN101597520A CN101597520A CNA2009100652678A CN200910065267A CN101597520A CN 101597520 A CN101597520 A CN 101597520A CN A2009100652678 A CNA2009100652678 A CN A2009100652678A CN 200910065267 A CN200910065267 A CN 200910065267A CN 101597520 A CN101597520 A CN 101597520A
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Abstract
The present invention discloses a kind of hydrocarbon hydro-conversion method, oil with enter thick desulphurization reactor after hydrogen mixes, 150～500 ℃ of pressure 0.70～21MPa, temperature, the volume ratio 100～3000: 1 of hydrogen oil, air speed 0.1～25.0hr
-1With the catalyzer contact reacts, reaction effluent enters dark desulfurization and conversion reactor after removing hydrogen sulfide under the condition, and 150～500 ℃ of pressure 0.70～21MPa, temperature, the volume ratio of hydrogen oil is 100～3000: 1, air speed 0.1～25.0hr
-1Reaction conditions contact down and carry out dark desulfurization and conversion reaction with catalyzer, the air speed of reactor can improve 2%～50%.
Description
Technical field
The present invention relates to hydro carbons process for purification in the presence of hydrogen, particularly reduce the method for hydro carbons sulphur content by hydrodesulfurizationof of hydrocarbons.
Technical background
The hydrocarbon hydroconversion process be raw material hydrocarbon in High Temperature High Pressure, face and carry out in the presence of hydrogen and the catalyzer that hydrogenation, desulfurization, denitrogenation, molecular structure are reset and a kind of catalytic conversion process of reaction such as cracking, it is the reaction process of a consumption hydrogen, heat release, here said hydrocarbon hydroconversion process, its raw material hydrocarbon can be the hydro carbons from oil or coal or oil shale, the cut scope of raw material hydrocarbon from gasoline, kerosene, diesel oil, wax oil up to residual oil, and above-mentioned raw materials sulfur-bearing all in most cases.The hydrocarbon hydroconversion process is being classified as hydrotreatment process, unifining process and hydrocracking process traditionally, though there is no significant line of delimitation between these three kinds of hydroconversion process, well-known difference is arranged on the depth of conversion of raw material.The hydrotreatment process is that demulcent is a kind of in above-mentioned three class processes.The application of unifining process is more extensive than the hydrotreatment process, and also comprised the hydrotreatment process in a broad sense, typical unifining process comprises the hydrogenating desulfurization and the hydrodenitrification of hydrocarbon raw material, is exactly a kind of important unifining process as hydrogenating desulfurization.Hydrocracking process be in above-mentioned three class processes hydrocarbon raw material by maximum a kind of of cracked, it is a raw material with gasoline, kerosene, diesel oil, wax oil and residual oil, is widely used in production liquefied petroleum gas (LPG), catalytic reforming raw material, high-quality intermediate oil, cracking ethylene raw material, WHITE OIL PRODUCTION raw material and lubricated wet goods.The related all kinds of devices of hydrocracking are a kind of process units that integrate catalyzed reaction technology, pressure technique and oil Refining Technologies, and the characteristics such as oily scope is wide, product structure flexible, good product quality, liquid yield height that process raw material with it become the key means of the production of balance refinery and the market requirement day by day.
The technical process of hydrocracking generally is divided into reactive moieties and fractionation part.When dividing by the streams preface, reactive moieties can be divided into: raw material supercharging, heating and cooling and reaction, three parts of gas-liquid separation.A typical conversion zone independently, generally include following several key equipment: conversion unit comprises one or more reactors; Intensification, cooling system comprise process furnace, interchanger and air-cooler, watercooler; Gas-liquid separation equipment comprises high-pressure separator, light pressure separator; Rotating machinery comprises that make-up hydrogen compressor, circulating hydrogen compressor, high pressure feedstock oil pump, high pressure generate equipment such as oily energy recovery hydraulic turbine pump.
A main purpose of hydroconversion process removes various heteroatomss in the stock oil exactly, and sulfide and nitride are most important non-hydrocarbons components in the oil, and its quantity, type and distribution directly influence the selection of the course of processing and operational condition.In hydroconversion process, the hydrogenation reaction of sulfocompound is active to have confidential relation with its molecular structure, and the reactive behavior of thiophene sulphur compound is minimum, and hydrogenating desulfurization is the most difficult when wherein containing three rings with dibenzothiophene.Hydrogen sulfide that produces in the hydroconversion process and thiophene will be competed on a kind of active centre at catalyzer, and the existence of a large amount of hydrogen sulfide has to a certain degree restraining effect to hydrodenitrification and aromatic ring hydrogenation.This shows that the hydrogen sulfide that produces in the hydroconversion process makes production super low sulfur cleaning product difficulty more to a certain extent, or even impossible.
Summary of the invention
The present invention proposes a kind of hydrocarbon hydro-conversion method, with circulation gas the hydrogen sulfide stripping in the reaction product is come out, reduce the hydrogen sulfide content that reaction generates, the existence that reduces hydrogen sulfide has to a certain degree restraining effect, production super low sulfur cleaning product to hydrodenitrification and aromatic ring hydrogenation.
A kind of hydrocarbon hydro-conversion method of the present invention is characterized in that: hydro carbons with enter thick desulphurization reactor after hydrogen mixes, 150～500 ℃ of pressure 0.70～21MPa, temperature, the volume ratio 100～3000: 1 of hydrogen oil, air speed 0.1～25.0hr
-1Contact with catalyzer under the condition and carry out thick desulphurization reaction, reaction effluent enters dark desulfurization and conversion reactor behind stripping, and 150～500 ℃ of pressure 0.70～21MPa, temperature, the volume ratio of hydrogen oil is 100～3000: 1, air speed 0.1～25.0hr
-1Reaction conditions contact down and carry out dark desulfurization-hydrogenation conversion reaction with catalyzer, obtain product.
Stripping medium of the present invention is hydrogen, nitrogen, circulating hydrogen, is preferably hydrogen.
Describedly after hydrogen stripped, enter dark desulfurization-hydrogenation conversion reactor from the effusive reaction effluent of thick desulphurization reactor.
Described reaction feed contacts hydrocarbon saturated reaction and reactions such as aromatic hydrocarbons open loop and macromolecular cleavage such as carry out desulfurization, denitrogenation, deoxidation, removing heavy-metal, alkene is saturated, aromatic hydrocarbons is saturated with catalyzer in thick desulphurization reactor.
Described stripping working pressure is than the low 0.005～1.0MPa of working pressure of thick desulphurization reaction.
Described thick desulfurization is identical with the deep desulfuration reactor operating condition or different.
The present invention's effluent that sulfide hydrogen in the thick desulphurization reactor is higher carries out the content that stripping reduces hydrogen sulfide, and it reduces the restraining effect of its follow-up hydrodesulphurisatioreactors reactors, can adopt different stripping gases according to practical situation, and the present invention recommends to adopt recycle hydrogen.Can the part light hydrocarbon component be stripped in the stripping overhead gas to guarantee to remove to greatest extent hydrogen sulfide according to practical situation.
The present invention sends into low in hydrogen sulphide concentration or even not hydrogen sulfide containing reaction effluent and carries out the deep desulfuration reaction in the deep desulfuration reactor, owing to eliminated the disadvantageous effect of hydrogen sulfide, can make it under than religion demulcent operational condition, obtain the super low sulfur cleaning product.
The used catalyzer of hydroconversion process is a non-precious metal catalyst, is active ingredient with the base metal, as: metal component is group vib metal and VIII family metal, as tungsten or molybdenum, cobalt and nickel, metal are to exist with oxidation state or sulphided state, and carrier is aluminum oxide or molecular sieve.
The normally common non-precious metal catalyst of the hydrogenation conversion catalyst that the present invention relates to, hydrogenation conversion catalyst is the molecular sieve type hydrogenation conversion catalyst normally, also can be amorphously to mix the molecular sieve type hydrogenation conversion catalyst, or the amorphous type catalyzer.Hydrogenation conversion catalyst does not require to have high anti-nitrogen ability.
Described hydrocarbon hydroconversion process comprises hydrotreatment, hydrofining and hydrocracking process.
Described hydrofining comprises: raw material hydrofining and hydrogenation of net product are refining, mainly carry out hydrogenating desulfurization, hydrodenitrification, hydrodemetallation (HDM), hydrogenation aromatics-removing, hydrogenation is saturated and hydrogenation takes off reactions such as impurity.
Described hydrotreatment comprises: mainly be the hydrotreatment to raw material, mainly carry out hydrogenating desulfurization, hydrodenitrification, hydrodemetallation (HDM) and the reaction of hydrogenation holder impurity, for subsequent technique provides high quality raw material.
Described hydrocracking comprises: single hop technology, single hop polyphone technology, two-stage process journey, inverted sequence technology, once by technological processs such as technology, part circulation technology, recycle to extinction technologies.
Process conditions of the present invention and conventional hydroconversion process are compared and are relaxed or identical, and can adjust according to feedstock property, product requirement etc. on experiment or mimic basis.
Adopt technical solution of the present invention to have following beneficial effect:
1) indication method of the present invention adopts demulcent service temperature more, has reduced the once investment and the operation processing charges of device.
2) indication method of the present invention adopts demulcent working pressure more, has reduced the once investment and the operation processing charges of device.
3) indication method of the present invention has reduced steam oil ratio (SOR), has reduced the once investment and the operation processing charges of device.
4) floor space of minimizing device.
5) be applicable to that existing apparatus transform production super low sulfur cleaning product as, high-pressure section is transformed minimum
6) air speed of reactor can improve 2%～50%.
Below in conjunction with accompanying drawing technical solution of the present invention is elaborated, but do not limit the present invention.
Description of drawings
Fig. 1: a kind of typical flowchart of the present invention.
1 thick desulphurization reactor, 2 stripping towers, 3 deep desulfuration reactors, 4 separators, 5 take off the liquid facility, 6 desulphurization of recycle hydrogen facilities, 7 hydrogen gas compressors, 8 stock oils, 9 reaction feed, 10 reaction effluents, 11 stripping overhead gases, oil at the bottom of 12 stripping towers, 13 reaction effluents, 14 separator top gas, 15 separator liquid, 16 sulfur-bearing recycle hydrogens, 17 desulphurization circulating hydrogen, 18 recycle hydrogens, 19 new hydrogen, 20 recycle hydrogens
Embodiment
Below in conjunction with accompanying drawing technical solution of the present invention is elaborated, accompanying drawing not delimit the scope of the invention just for the present invention is described.
As shown in Figure 1, stock oil 8 and recycle hydrogen 20 are mixed into reaction feed 9, and reaction feed 9 enters carries out the thick desulphurization reaction of hydrogenation in the thick desulphurization reactor 1, and the reaction effluent 10 that comes out from thick desulphurization reactor 1 enters stripping tower 2 and takes off H
2S, stripping tower 2 adopts recycle hydrogen 20 as the stripping medium, removes H
2Enter deep desulfuration reactor 3 after oil 12 and recycle hydrogen 20 mix at the bottom of the stripping tower behind the S and carry out dark desulfurization and conversion reaction, the reaction effluent 13 that comes out from deep desulfuration reactor 3 enters separator 4 to be separated, parting liquid 15 is sent into follow-up system and is handled, enter after separating gas 14 and stripping overhead gas 11 mixing and take off liquid facility 5, sulfur-bearing recycle hydrogen 16 enters desulphurization of recycle hydrogen facility 6 and carries out desulphurization of recycle hydrogen, recycle hydrogen 17 enters hydrogen gas compressor 7 after the desulfurization, and recycle hydrogen 18 is mixed into recycle hydrogen 20 with new hydrogen 19.
Claims (8)
1. hydrocarbon hydro-conversion method is characterized in that: hydrocarbon ils with enter thick desulphurization reactor after hydrogen mixes, 150～500 ℃ of pressure 0.70～21MPa, temperature, the volume ratio 100～3000: 1 of hydrogen oil, air speed 0.1～25.0hr
-1With the catalyzer contact reacts, reaction effluent enters dark desulfurization and conversion reactor after removing hydrogen sulfide under the condition, and 150～500 ℃ of pressure 0.70～21MPa, temperature, the volume ratio of hydrogen oil is 100～3000: 1, air speed 0.1～25.0hr
-1Reaction conditions contact down and carry out dark desulfurization and conversion reaction with catalyzer.
2. according to the described a kind of hydrocarbon hydro-conversion method of claim 1, it is characterized in that: utilize the rare gas element stripping to remove the part or all of hydrogen sulfide of reaction effluent.
3. according to the described a kind of hydrocarbon hydro-conversion method of claim 1, it is characterized in that: utilize flash distillation to remove the part or all of hydrogen sulfide of reaction effluent.
4. according to the described a kind of hydrocarbon hydro-conversion method of claim 1, it is characterized in that: catalyzer is an active ingredient with group vib metal and VIII family metal, with aluminum oxide or molecular sieve carrier.
5. according to the described a kind of hydrocarbon hydro-conversion method of claim 1, it is characterized in that: catalyzer is an active ingredient with at least a in tungsten, molybdenum, cobalt, the nickel.
6. according to the described a kind of hydrocarbon hydro-conversion method of claim 2, it is characterized in that: rare gas element is a kind of in hydrogen-containing gas, nitrogen, the water vapor.
7. according to the described a kind of hydrocarbon hydro-conversion method of claim 2, it is characterized in that: rare gas element is a hydrogen-containing gas.
8. according to the described a kind of hydrocarbon hydro-conversion method of claim 2, it is characterized in that: the working pressure of the thick desulphurization reaction of stripping pressure ratio hangs down 0.005～1.0MPa.
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| CNA2009100652678A CN101597520A (en) | 2009-06-25 | 2009-06-25 | A kind of hydrocarbon hydro-conversion method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102604673A (en) * | 2011-01-20 | 2012-07-25 | 中国石油化工股份有限公司 | Method for producing low-sulfur gasoline |
| CN102703109A (en) * | 2012-05-30 | 2012-10-03 | 中国石油集团工程设计有限责任公司北京分公司 | Method for removing sulfur from crude oil by gas stripping method |
-
2009
- 2009-06-25 CN CNA2009100652678A patent/CN101597520A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102604673A (en) * | 2011-01-20 | 2012-07-25 | 中国石油化工股份有限公司 | Method for producing low-sulfur gasoline |
| CN102604673B (en) * | 2011-01-20 | 2014-12-03 | 中国石油化工股份有限公司 | Method for producing low-sulfur gasoline |
| CN102703109A (en) * | 2012-05-30 | 2012-10-03 | 中国石油集团工程设计有限责任公司北京分公司 | Method for removing sulfur from crude oil by gas stripping method |
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Address after: 100728 Beijing, Chaoyangmen, North Street, No. 22, No. Applicant after: China Petrochemical Group Corp. Co-applicant after: Luoyang Petrochemical Engineering Corporation /SINOPEC Address before: 100728 Beijing, Chaoyangmen, North Street, No. 22, No. Applicant before: China Petrochemical Group Corp. Co-applicant before: Luoyang Petrochemical Engineering Co., China Petrochemical Group |
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Application publication date: 20091209 |