CN103897732A - High-nitrogen and high-aromatic hydrocarbon hydrogenation modification process and thermal cracking process combining method - Google Patents
High-nitrogen and high-aromatic hydrocarbon hydrogenation modification process and thermal cracking process combining method Download PDFInfo
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- CN103897732A CN103897732A CN201410106621.8A CN201410106621A CN103897732A CN 103897732 A CN103897732 A CN 103897732A CN 201410106621 A CN201410106621 A CN 201410106621A CN 103897732 A CN103897732 A CN 103897732A
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Abstract
The invention discloses a high-nitrogen and high-aromatic hydrocarbon hydrogenation modification process and thermal cracking process combining method, which is capable of improving an overall light oil yield in a deep hydrogenation modification process of high heavy coal tar. Deep hydrogenation modification generated oil RHPO in the deep hydrogenation modification process RH of high-nitrogen and high-aromatic hydrocarbon F1 is separated to obtain deep hydrogenation modification wax oil RHP-VGO mainly consisting of hydrocarbon which is at 330-530 DEG C in conventional boiling point and deep hydrogenation modification tail oil RHP-VRO mainly consisting of hydrocarbon which is more than 530 DEG C in conventional boiling point; the RHP-VGO is applied to a hydrogenation cracking process RHC, while the RHP-VRO enters a thermal processing process RC where a thermal cracking reaction occurs to obtain thermal processing fraction oil RC-LO which is less than 530 DEG C in conventional boiling point and thermal processing heavy oil RC-HO which is more than 530 DEG C in conventional boiling point; the thermal processing fraction oil RC-LO or the thermal processing heavy oil RC-HO enters the deep hydrogenation modification process RH to get into contact with a hydrogenation modification catalyst.
Description
Technical field
The present invention relates to a kind of high nitrogen high aromatic hydrogenation upgrading process and thermal cracking process combined method, say especially, the present invention relates to a kind of coal tar hydrogenation modification process and thermal cracking process combined method, for the lighting processing of heavy coal tar, can improve the overall yield of light oil of the deep hydrogenation upgrading process of heavy coal tar, the deep hydrogenation upgrading that separates the high aromatic hydrocarbons F1 of high nitrogen deep hydrogenation upgrading process RH generates the deep hydrogenation upgrading wax oil RHP-VGO that the oily RHPO hydrocarbon that to obtain be mainly 330～530 DEG C by conventional boiling point forms, mainly be greater than by conventional boiling point the deep hydrogenation upgrading tail oil RHP-VRO that the hydrocarbon of 530 DEG C forms, deep hydrogenation upgrading wax oil RHP-VGO removes hydrocracking process RHC, deep hydrogenation upgrading tail oil RHP-VRO enters the hot procedure RC that comprises heat cracking reaction and obtains the hot-work heavy oil RC-HO that conventional boiling point is greater than 530 DEG C lower than the hot-work distillate RC-LO of 530 DEG C and conventional boiling point, hot-work distillate RC-LO with or hot-work heavy oil RC-HO penetration depth hydro-upgrading process RH contact with catalyst for hydro-upgrading.
Background technology
In poor quality, the full cut of coalite tar is wide fraction oil product, comprise conventional boiling point that molecular dimension is little and lower than the cut (contained aromatic hydrocarbons is monocycle) of 200 DEG C and the medium conventional boiling point of molecular dimension be the cut (containing 2～6 Polycyclic aromatic hydrocarbons) of 200～530 DEG C, conventionally also comprising the conventional boiling point that molecular dimension is large (contains 7 rings and above aromatic hydrocarbons thereof higher than the cut of 530 DEG C, colloid, bituminous matter) be heavy coal-tar pitch component, according to the difference of the hot procedure operational condition of coalite tar in coal and generation, quantity and the nature difference of the contained heavy coal-tar pitch of middle coalite tar are larger, comprise conventional boiling point is greater than the hydroconversion process that the coal tar component of 530 DEG C and conventional boiling point be less than the coal tar of the coal tar component of 530 DEG C and generates oil to comprise conventional boiling point be the degree of depth RHP-VRO that the deep hydrogenation upgrading wax oil RHP-VGO of 350～530 DEG C and conventional boiling point are greater than 530 DEG C such as containing wide variety of conventional boiling point and be greater than coalite tar in the full cut of coal tar component of 530 DEG C and produce the hydrofining of the hydroconversion process of diesel component simultaneously, current working method is conventional boiling point to be greater than to the deep hydrogenation upgrading heavy oil RHP-M of 350 DEG C process as a mixed fraction RHP-M.
The first processing scheme of mixed fraction RHP-M is to produce the small molecules products such as diesel oil as hydrocracking raw material, but the molecular dimension difference in size of deep hydrogenation upgrading tail oil RHP-VRO that is greater than 530 DEG C due to the deep hydrogenation upgrading wax oil RHP-VGO of 350～530 DEG C and conventional boiling point is larger, its cracking is that the hydrocracking depth difference of diesel oil is larger, optimized catalyst formulation and service temperature, working pressure, catalyzer air speed differs greatly, cannot realize optimized operation: to the operational condition of deep hydrogenation upgrading wax oil RHP-V6O the best to the deep hydrogenation upgrading tail oil RHP-VRO cracking insufficiency of function that seems, cause the too small cracking rate of deep hydrogenation upgrading tail oil RHP-VRO, finally strengthen the stock oil process scale of cracking process, cause investment to be risen serious, operational condition to deep hydrogenation upgrading tail oil RHP-VRO the best seems that to deep hydrogenation upgrading wax oil RHP-VGO cracking function is excessive, cause that deep hydrogenation upgrading wax oil RHP-VGO liquid yield is low and gas yield is high, and because initial cracking excess Temperature causes the operational cycle short.The initial hydrocracking temperature of hydro-upgrading tail oil RHP-VRO is conventionally higher 40～50 DEG C than the initial hydrocracking temperature of deep hydrogenation upgrading wax oil RHP-VGO.
The second processing scheme of mixed fraction RHP-M is as small molecules products such as non-hydrogen thermally splitting raw material production diesel oil, but because the deep hydrogenation upgrading wax oil RHP-VGO of 350～530 DEG C belongs to good hydrocracking raw material, therefore reduced the value of deep hydrogenation upgrading wax oil RHP-VGO, formed waste.
Above analytic explanation, reply deep hydrogenation upgrading wax oil RHP-VGO and deep hydrogenation upgrading tail oil RHP-VRO process respectively, indicated on the one hand the improvement direction of catalyzer, indicated on the one hand the improvement direction of operating procedure, the present invention proposes improving one's methods of a kind of operating procedure.
The above-mentioned technological deficiency that is present in low grade coal tar deep hydrogenation upgrading process, is present in the deep hydrogenation upgrading process of the high aromatic hydrocarbons F1 of similar high nitrogen equally.The high aromatic hydrocarbons F1 of high nitrogen can be the high aromatic hydrocarbons of any high nitrogen, as long as the deep hydrogenation upgrading of its deep hydrogenation upgrading process RH generates, in oily RHPO, to contain conventional boiling point be the plus depth hydro-upgrading tail oil cut that the deep hydrogenation upgrading wax oil cut of 330～530 DEG C and conventional boiling point are greater than 530 DEG C; The high aromatic hydrocarbons F1 of high nitrogen, can be selected from one or more in following material:
1. coalite tar or its distillate or its hot procedure gained oil product;
2. coal-tar middle oil or its distillate or its hot procedure gained oil product;
3. coal-tar heavy oil or its distillate or its hot procedure gained oil product;
4. gelatin liquefaction process gained liquefied coal coil or its distillate or its hot procedure gained oil product; ;
5. shale oil or its distillate or its hot procedure gained oil product;
6. tar sand basic weight oil or its hot procedure gained oil product;
7. ethylene cracking tar;
8. thermally splitting tar;
9. petroleum base heavy oil thermal course of processing gained heavy oil fraction product, hot procedure is coking heavy oil process or heavy oil catalytic cracking process or heavy oil catalytic pyrolysis process;
The hydrocarbon ils of gluey pitch shape component that what 10. other aromaticity content was high be rich in.
The conception of a kind of high nitrogen high aromatic hydrogenation upgrading process of the present invention and thermal cracking process combined method is: in order to improve the overall yield of light oil of deep hydrogenation upgrading process RH of heavy coal tar F1, the deep hydrogenation upgrading that separates coal tar F1 deep hydrogenation upgrading process RH generates the deep hydrogenation upgrading wax oil RHP-VGO that the oily RHPO hydrocarbon that to obtain be mainly 330～530 DEG C by conventional boiling point forms, mainly be greater than by conventional boiling point the deep hydrogenation upgrading tail oil RHP-VRO that the hydrocarbon of 530 DEG C forms, deep hydrogenation upgrading wax oil RHP-VGO removes hydrocracking process RHC, deep hydrogenation upgrading tail oil RHP-VRO enters the hot procedure RC that comprises heat cracking reaction and obtains the hot-work heavy oil RC-HO that conventional boiling point is greater than 530 DEG C lower than the hot-work distillate RC-LO of 530 DEG C and conventional boiling point, hot-work distillate RC-LO with or hot-work heavy oil RC-HO penetration depth hydro-upgrading process RH contact with catalyst for hydro-upgrading, deep hydrogenation upgrading process RH processes the generation oil of heavy coal tar F1 and hot procedure RC simultaneously, has formed combination process.
The method of the invention has no report.
Therefore, the first object of the present invention is to propose a kind of high nitrogen high aromatic hydrogenation upgrading process and thermal cracking process combined method, and the high aromatic hydrocarbons deep hydrogenation of high nitrogen upgrading generates oil and comprises the deep hydrogenation upgrading tail oil RHP-VRO that conventional boiling point is greater than 530 DEG C.
The second object of the present invention is to propose a kind of coal tar hydrogenation modification process and thermal cracking process combined method, and coal tar deep hydrogenation upgrading generates oil and comprises the deep hydrogenation upgrading tail oil RHP-VRO that conventional boiling point is greater than 530 DEG C.
Summary of the invention
A kind of high nitrogen high aromatic hydrogenation upgrading process of the present invention and thermal cracking process combined method, is characterized in that comprising following steps:
The high aromatic hydrocarbons F1 of high nitrogen is converted into deep hydrogenation upgrading reaction effluent RHP at deep hydrogenation upgrading process RH; Separation deep hydrogenation upgrading reaction effluent RHP obtains deep hydrogenation upgrading and generates oily RHPO; Separating deep hydrogenation upgrading generates deep hydrogenation upgrading wax oil RHP-VGO that the oily RHPO hydrocarbon that to obtain be mainly 330～530 DEG C by conventional boiling point form, is mainly greater than by conventional boiling point deep hydrogenation upgrading tail oil RHP-VRO and the deep hydrogenation upgrading benzoline RHP-LMO that the hydrocarbon of 530 DEG C forms; It is the hydrocracking wax oil RHCP-VGO of 330～530 DEG C lower than the hydrocracking lighting end RHCP-LMO of 330 DEG C and conventional boiling point that deep hydrogenation upgrading wax oil RHP-VGO goes hydrocracking process RHC to produce conventional boiling point; Deep hydrogenation upgrading tail oil RHP-VRO enters and the hot procedure RC of heat cracking reaction occurs obtains the hot-work heavy oil RC-HO that conventional boiling point is greater than 530 DEG C lower than the hot-work distillate RC-LO of 530 DEG C and conventional boiling point, hot-work distillate RC-LO with or hot-work heavy oil RC-HO penetration depth hydro-upgrading process RH contact with catalyst for hydro-upgrading.
For simple flow, the separate part of the hydrocracking reaction effluent RHCP penetration depth hydro-upgrading reaction effluent RHP of the hydrocracking process RHC of working depth hydro-upgrading wax oil RHP-VGO.
At least a portion hydrocracking wax oil RHCP-VGO returns to hydrocracking process RHC and forms circulation hydrocracking flow process.
The high aromatic hydrocarbons F1 of high nitrogen of the present invention's processing, can be selected from one or more in following material:
1. coalite tar or its distillate or its hot procedure gained oil product;
2. coal-tar middle oil or its distillate or its hot procedure gained oil product;
8. coal-tar heavy oil or its distillate or its hot procedure gained oil product;
4. gelatin liquefaction process gained liquefied coal coil or its distillate or its hot procedure gained oil product; ;
5. shale oil or its distillate or its hot procedure gained oil product;
6. tar sand basic weight oil or its hot procedure gained oil product;
7. ethylene cracking tar;
8. thermally splitting tar;
9. petroleum base heavy oil thermal course of processing gained heavy oil fraction product, hot procedure is coking heavy oil process or heavy oil catalytic cracking process or heavy oil catalytic pyrolysis process;
The hydrocarbon ils of gluey pitch shape component that what 10. other aromaticity content was high be rich in.
When the high aromatic hydrocarbons F1 of the high nitrogen of the present invention is coal tar, the cetane value of the diesel oil distillate in coal tar deep hydrogenation upgrading reaction effluent RHP is conventionally greater than 28, is generally greater than 36, more preferably greater than 40.
Embodiment
Below describe the present invention in detail.
Pressure of the present invention is absolute pressure.
Conventional boiling point of the present invention refers to the vapor-liquid equilibrium temperature of material under a barometric point.
Impurity composition of the present invention refers to the hydride of non-hydrocarbon component in stock oil as water, ammonia, hydrogen sulfide, hydrogenchloride etc.
Conventional gas hydrocarbon of the present invention refers to the hydro carbons that is gaseous state under normal condition, comprises methane, ethane, propane, butane.
Conventional liq hydrocarbon of the present invention refers to the hydro carbons being in a liquid state under normal condition, comprises the hydro carbons that pentane and boiling point thereof are higher.
Proportion of the present invention, unless stated otherwise, refers to the ratio of fluid density and normal pressure under normal pressure, 15.6 DEG C of conditions, 15.6 DEG C of Water Under density.
Petroleum naphtha component of the present invention refers to conventional boiling point lower than the conventional liq hydrocarbon of 200 DEG C.
It is the hydro carbons of 200～375 DEG C that diesel component of the present invention refers to conventional boiling point.
The composition of component of the present invention or concentration or content or yield value, unless stated otherwise, be weight basis value.
The high aromatic hydrocarbons F1 of high nitrogen of the present invention can be the coal tar from pyrolysis of coal or coal generating gas process.Coal tar of the present invention can be coalite tar, coal-tar middle oil, coal-tar heavy oil cut and mixing oil thereof.Because the processing condition of raw coal character, pyrolysis of coal or coal generating gas process all change within the specific limits, coal tar oil properties also changes within the specific limits, the processing condition of coal-tar heavy oil primary distillation process and product requirement also change within the specific limits, therefore the character of coal-tar heavy oil cut also changes within the specific limits.Hydrogenating materials coal tar oil properties of the present invention, conventional boiling point is generally 50～650 DEG C and is generally 60～550 DEG C, proportion is generally 0.91～1.22, water-content is generally 0.2～5.0%, and conventionally metal content is that 2～80PPm, sulphur content are 0.4～0.8%, nitrogen content is 0.4～1.8%, oxygen level is 0.4～8.0%.
The high aromatic hydrocarbons of high nitrogen of the present invention, it can be any suitable raw material hydrocarbon, refer specifically to and comprise conventional boiling point simultaneously and be greater than the coal tar that the coal tar component of 530 DEG C and conventional boiling point are less than the coal tar component of 530 DEG C, now raw material hydrocarbon is selected from the full cut of coal-tar middle oil or the full cut of coalite tar or coal-tar middle oil part cut or coalite tar part cut; Raw material hydrocarbon can be also the coal tar that removes specific components, is selected from and removes the coal tar of phenol component or remove the coal tar of naphthalene component or remove the coal tar of anthracene component.
A kind of high nitrogen high aromatic hydrogenation upgrading process of the present invention and thermal cracking process combined method, is characterized in that comprising following steps:
The high aromatic hydrocarbons F1 of high nitrogen is converted into deep hydrogenation upgrading reaction effluent RHP at deep hydrogenation upgrading process RH; Separation deep hydrogenation upgrading reaction effluent RHP obtains deep hydrogenation upgrading and generates oily RHPO; Separating deep hydrogenation upgrading generates deep hydrogenation upgrading wax oil RHP-VGO that the oily RHPO hydrocarbon that to obtain be mainly 330～530 DEG C by conventional boiling point form, is mainly greater than by conventional boiling point deep hydrogenation upgrading tail oil RHP-VRO and the deep hydrogenation upgrading benzoline RHP-LMO that the hydrocarbon of 530 DEG C forms; It is the hydrocracking wax oil RHCP-VGO of 330～530 DEG C lower than the hydrocracking lighting end RHCP-LMO of 330 DEG C and conventional boiling point that deep hydrogenation upgrading wax oil RHP-VGO goes hydrocracking process RHC to produce conventional boiling point; Deep hydrogenation upgrading tail oil RHP-VRO enters and the hot procedure RC of heat cracking reaction occurs obtains the hot-work heavy oil RC-HO that conventional boiling point is greater than 530 DEG C lower than the hot-work distillate RC-LO of 530 DEG C and conventional boiling point, hot-work distillate RC-LO with or hot-work heavy oil RC-HO penetration depth hydro-upgrading process RH contact with catalyst for hydro-upgrading.
For simple flow, the separate part of the hydrocracking reaction effluent RHCP penetration depth hydro-upgrading reaction effluent RHP of the hydrocracking process RHC of working depth hydro-upgrading wax oil RHP-VGO.
At least a portion hydrocracking wax oil RHCP-VGO returns to hydrocracking process RHC and forms circulation hydrocracking flow process.
The high aromatic hydrocarbons F1 of high nitrogen of the present invention's processing, can be selected from one or more in following material:
1. coalite tar or its distillate or its hot procedure gained oil product;
2. coal-tar middle oil or its distillate or its hot procedure gained oil product;
3. coal-tar heavy oil or its distillate or its hot procedure gained oil product;
4. gelatin liquefaction process gained liquefied coal coil or its distillate or its hot procedure gained oil product; ;
5. shale oil or its distillate or its hot procedure gained oil product;
6. tar sand basic weight oil or its hot procedure gained oil product;
7. ethylene cracking tar;
8. thermally splitting tar;
9. petroleum base heavy oil thermal course of processing gained heavy oil fraction product, hot procedure is coking heavy oil process or heavy oil catalytic cracking process or heavy oil catalytic pyrolysis process;
The hydrocarbon ils of gluey pitch shape component that what 10. other aromaticity content was high be rich in.
When the high aromatic hydrocarbons F1 of the high nitrogen of the present invention is coal tar, the cetane value of the diesel oil distillate in coal tar deep hydrogenation upgrading reaction effluent RHP is conventionally greater than 28, is generally greater than 36, more preferably greater than 40.
Claims (8)
1. the high aromatic hydrogenation upgrading of high nitrogen and a thermal cracking process combined method, is characterized in that comprising following steps:
The high aromatic hydrocarbons F1 of high nitrogen is converted into deep hydrogenation upgrading reaction effluent RHP at deep hydrogenation upgrading process RH; Separation deep hydrogenation upgrading reaction effluent RHP obtains deep hydrogenation upgrading and generates oily RHPO; Separating deep hydrogenation upgrading generates deep hydrogenation upgrading wax oil RHP-VGO that the oily RHPO hydrocarbon that to obtain be mainly 330～530 DEG C by conventional boiling point form, is mainly greater than by conventional boiling point deep hydrogenation upgrading tail oil RHP-VRO and the deep hydrogenation upgrading benzoline RHP-LMO that the hydrocarbon of 530 DEG C forms; It is the hydrocracking wax oil RHCP-VGO of 330～530 DEG C lower than the hydrocracking lighting end RHCP-LMO of 330 DEG C and conventional boiling point that deep hydrogenation upgrading wax oil RHP-VGO goes hydrocracking process RHC to produce conventional boiling point; Deep hydrogenation upgrading tail oil RHP-VRO enters and the hot procedure RC of heat cracking reaction occurs obtains the hot-work heavy oil RC-HO that conventional boiling point is greater than 530 DEG C lower than the hot-work distillate RC-LO of 530 DEG C and conventional boiling point, hot-work distillate RC-LO with or hot-work heavy oil RC-HO penetration depth hydro-upgrading process RH contact with catalyst for hydro-upgrading.
2. method according to claim 1, is characterized in that:
The hydrocracking reaction effluent RHCP of the hydrocracking process RHC of working depth hydro-upgrading wax oil RHP-VGO, the separate part of penetration depth hydro-upgrading reaction effluent RHP.
3. method according to claim 1, is characterized in that:
At least a portion hydrocracking wax oil RHCP-VGO returns to hydrocracking process RHC and forms circulation hydrocracking flow process.
4. method according to claim 2, is characterized in that:
At least a portion hydrocracking wax oil RHCP-VGO returns to hydrocracking process RHC and forms circulation hydrocracking flow process.
5. according to the method described in claim 1 or 2 or 3 or 4, it is characterized in that:
The high aromatic hydrocarbons F1 of high nitrogen, can be selected from one or more in following material:
1. coalite tar or its distillate or its hot procedure gained oil product;
2. coal-tar middle oil or its distillate or its hot procedure gained oil product;
3. coal-tar heavy oil or its distillate or its hot procedure gained oil product;
4. gelatin liquefaction process gained liquefied coal coil or its distillate or its hot procedure gained oil product; ;
5. shale oil or its distillate or its hot procedure gained oil product;
6. tar sand basic weight oil or its hot procedure gained oil product;
7. ethylene cracking tar;
8. thermally splitting tar;
9. petroleum base heavy oil thermal course of processing gained heavy oil fraction product, hot procedure is coking heavy oil process or heavy oil catalytic cracking process or heavy oil catalytic pyrolysis process;
The hydrocarbon ils of gluey pitch shape component that what 10. other aromaticity content was high be rich in.
6. according to the method described in claim 1 or 2 or 3 or 4, it is characterized in that:
The high aromatic hydrocarbons F1 of high nitrogen is middle coalite tar, and the cetane value of the diesel oil distillate in coal tar deep hydrogenation upgrading reaction effluent RHP is greater than 28.
7. method according to claim 6, is characterized in that:
The high aromatic hydrocarbons F1 of high nitrogen is middle coalite tar, and the cetane value of the diesel oil distillate in coal tar deep hydrogenation upgrading reaction effluent RHP is greater than 36.
8. method according to claim 6, is characterized in that:
The high aromatic hydrocarbons F1 of high nitrogen is middle coalite tar, and the cetane value of the diesel oil distillate in coal tar deep hydrogenation upgrading reaction effluent RHP is greater than 40.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101684415A (en) * | 2008-09-27 | 2010-03-31 | 中国石油化工股份有限公司 | Hydrocracking method for producing chemical materials to maximum with low cost |
| CN102051222A (en) * | 2010-12-26 | 2011-05-11 | 何巨堂 | High-nitrogen high-aromatic-oil hydrogenation conversion method based on two-stage process |
| CN102071057A (en) * | 2010-12-29 | 2011-05-25 | 何巨堂 | Two-stage high-nitrogen high-aromatic oil hydro-conversion method |
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- 2014-03-18 CN CN201410106621.8A patent/CN103897732A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101684415A (en) * | 2008-09-27 | 2010-03-31 | 中国石油化工股份有限公司 | Hydrocracking method for producing chemical materials to maximum with low cost |
| CN102051222A (en) * | 2010-12-26 | 2011-05-11 | 何巨堂 | High-nitrogen high-aromatic-oil hydrogenation conversion method based on two-stage process |
| CN102071057A (en) * | 2010-12-29 | 2011-05-25 | 何巨堂 | Two-stage high-nitrogen high-aromatic oil hydro-conversion method |
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Application publication date: 20140702 |