CN102030603B - Process for carrying out pyridine removal and hydrogenating on coking crude benzol - Google Patents
Process for carrying out pyridine removal and hydrogenating on coking crude benzol Download PDFInfo
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- CN102030603B CN102030603B CN 201010574518 CN201010574518A CN102030603B CN 102030603 B CN102030603 B CN 102030603B CN 201010574518 CN201010574518 CN 201010574518 CN 201010574518 A CN201010574518 A CN 201010574518A CN 102030603 B CN102030603 B CN 102030603B
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Abstract
The invention provides a process carrying out pyridine removal and hydrogenating on coking crude benzol, which is characterized in that heavy benzol is removed from coking crude benzol; after light benzol carries out hybrid reaction with a pyridine-removal compound agent in a static mixer when the heat exchange is carried out on the light benzol until the light benzol reaches to the normal temperature-78 DEG C, reaction products enter an electrofining setting tank for settling separation; sediments are discharged from the bottom of the settling tank; after pyridine-removal benzol is settled in the electric setting tank; refined crude benzol enters a hydrogenation unit to carry out hydrofining treatment after the heat exchange is carried out by a heat exchanger to make the temperature of the refined crude benzol reach 60-500 DEG C. Obtained liquid benzol enters a benzol separation system to obtain products: refined benzol, methylbenzene and dimethylbenzene.
Description
Technical field
The invention belongs to chemical technology field, particularly is the technology of feedstock production refining benzene with the coking benzene.
Background technology
The byproduct coking crude benzene that produces in the coal tar process is the important industrial chemicals of producing benzene (B), toluene (T), dimethylbenzene (X).Contain a large amount of unsaturated hydrocarbons and sulfur-bearing nitrogenous compound in the coal coking benzene, as straight-chain paraffin mercaptan, aromatic base mercaptan, thioether, thiophene, dibenzothiophene, benzo-thiophene, pyridine, picoline and lutidine etc.BTX is during as the basic Organic Chemicals of one-level, and these impurity need remove, thereby reach the purpose of purification.
At present, the method for crude benzene refining has three kinds: sulfuric acid method for making, extraction fractional distillation and hydrofining.The sulfuric acid treatment method is simple to operate, but has that degree of purification is low, the benzene yield is low and problem such as acid sludge is difficult, and environmental issue is outstanding, is eliminated gradually; Extraction fractional distillation exist energy consumption height, quality product be difficult to control, to problem such as the low coking crude benzene of thiophene content is inapplicable; The quality product height that hydrofining obtains, the aromatic hydrocarbons loss is little, becomes the main flow trend of crude benzene refining gradually.
The external technology that is used for the coking crude benzene shortening mainly contains Axens low temperature (320 ℃～380 ℃) the gas-liquid two-phase hydrogenation method of the U.S., the Uhde low temperature gas phase hydrogenation method of Germany and high temperature (600 ℃～630 ℃) the high pressure vapor hydrogenation Litol method of Japan.The refining level of external crude benzole hydrogenation is higher, mainly be the quality that relies on its catalyzer, and high-temperature and high-pressure hydrogenation is very high to material and the specification of quality of device, manufacture difficulty is very big with investment, operation running risk is relatively large, bears all being difficult on the general business economic.
Chinese patent CN1948244A discloses a kind of technology by coking benzene hydrogenation desulfurization denitrogenation producing refined benzene, mainly comprises coking benzene pre-treatment rectification step, three grades of desulfurized steps, purification step etc.Chinese patent CN101486623A discloses a kind of hydrofinishing method for crude benzol, the coking crude benzene raw material is after pre-treatment, after taking off heavily, decompression carries out pre-hydrotreating reaction and main hydrogenation reaction, gaseous phase materials after the hydrogenation reaction enters hp flash drum, isolate hydrogen-rich gas, liquid phase enters stabilizer tower and removes low boiling hydrocarbon, enters aromatic extraction unit at last, extracting obtains highly purified triphen, the problem that exists the catalyst for pre-hydrogenation bed pressure drop to raise.Chinese patent CN101519338A discloses a kind of process for hydrofining coking crude benzene, and, dimethylbenzene distillation unit refining by raw material pre-separation, hydrofining, fore-distillation, extractive distillation, aromatic hydrocarbons formed; This invention can reduce the aromatic hydrocarbons loss to a certain extent, and quality product can reach the quality of petroleum benzene.But no matter be external hydrogen addition technology or domestic hydrogen addition technology, all do not have after taking off heavily, separately the pyridines material to be removed, and pyridine compounds and their content height in the coal tar crude benzol in the conventional hydrogenation unit charging, these compounds are basic nitrogen compounds, severe inhibition the thiophenes hydrodesulfurization reaction, be the maximum inhibition of hydrodesulfurization reaction.They are vied each other by the hydrogenation approach in catalyst active center, and denitrification reaction is slower than desulphurization reaction, and nitride is trapped in the time ratio sulfide in active centre and will grows, and therefore can reduce desulfurization rate, and shorten the work-ing life of hydrogenation catalyst greatly.This shows, the pyridine compounds and their that pre-treatment removes in the hydrogenating materials is very necessary, and the denitrfying agent that provides with ZL94115190.5 or other acidic components denitrfying agent and denitrfying agent have bigger solubleness with pyridine compounds and their in crude benzol than in oil product, their residual meetings in crude benzol are adsorbed on catalyst surface, have reduced the surfactivity of expensive hydrogenation catalyst.
The objective of the invention is to reduce pyridine compounds and their to the influence of coking crude benzole hydrogenation desulfurization, under commercial benzene condition identical in quality, the mild hydrogenation condition improves air speed, increases treatment capacity; Under the constant situation of purification condition, improve the quality of commercial benzene, improve desulfurization, nitric efficiency.This patent is used takes off denitrfying agent that pyridine compounds and their can provide for ZL94115190.5 with agent or other effectively takes off the pyridine compounds and their agent.
Wherein the denitrfying agent that provides of the ZL94115190.5 that uses of the present invention by: be made up of A acidizer, B complexing agent and C solvent, A is the mixture that acidizer is selected from metaphosphoric acid, ortho-phosphoric acid, tetra-sodium, diacetyl oxide, pyromellitic acid anhydride or any two kinds of components; B is the mixture that complexing agent is selected from thiophosphoric anhydride, phosphorus trioxide, six tetraphosphine oxides, Vanadium Pentoxide in FLAKES or any two kinds of components; C is the mixture that solvent is selected from water, ethanol or any two kinds of components; Three kinds of shared ratios of component are: A is 6-85%(wt), B is that 0.1-85% (wt) and C are 0.1-85%(wt).
Summary of the invention
A kind of is raw material with the coal tar crude benzol, by taking off the refining combination process that carries out the hydrofining processing again of pyridine compounds and their, it is characterized in that coking crude benzene (1) is removed heavy benzol in taking off heavies column (A), the light benzene heat exchange enters electrofining slurry tank (C) pyridine compounds and their carries out hybrid reaction with agent (2) in static mixer (B) after or/and the middle sedimentation of natural subsidence jar (D) divides slag with taking off to normal temperature～78 ℃, sediment (3) (4) from electrofining slurry tank (C) or/and slurry tank (D) bottom discharge, take off pyridine benzene (5) after interchanger (E) heat exchange to 60～500 ℃, enter hydrofining system (F) and carry out hydrogenation, product behind the hydrogenation (6) is through cooling, after the separation, the liquid benzene that obtains enters in the benzene separation system (G), obtains product purification benzene, toluene, dimethylbenzene (7).
Taking off pyridine compounds and their among the present invention is the 0.2%-5% of raw material with the adding weight percent of agent (2).
In hydrofining system (F) hydrogenation unit Hydrobon catalyst is housed among the present invention, catalyzer is to be carrier with aluminum oxide, amorphous silicon aluminium or molecular sieve, be main active ingredient with Co, Mo and Ni, the preferential Co-Mo catalyst series of selecting comprises with the Co-Mo catalyst series being all catalyzer of basic modification; Hydrofining system (F) hydrogenation temperature can be the arbitrary value between 80 ℃～630 ℃, and hydrogen to oil volume ratio is 100: 1～3000: 1, and volume space velocity is 0.1h
-1～15h
-1, the reaction stagnation pressure is 0.5Mpa～21Mpa.
The order of electrofining slurry tank (C) and slurry tank (D) can be exchanged among the present invention; Electrofining strength of electric field in the electrofining slurry tank (C) is at 0-2000 volt/cm
2Scope.
Taking off the pyridine compounds and their unit among the present invention can be also can be after taking off heavy constituent before the coal tar crude benzol takes off heavy constituent.
The pyridine compounds and their that takes off that the present invention adopts can be the denitrfying agent that ZL94115190.5 provides with agent, but is not limited to this denitrfying agent, can be existing denitrfying agent, and they are acid but do not comprise sulfuric acid, or the mixture of acid.The described hydrofining technology of this patent can be existing hydrofining technology, but is not limited to existing hydrofining technology, comprises the improvement of hydrofining technology.The isolation technique of benzaldehyde product separation system (G) is prior art.
Description of drawings
Fig. 1 is that coking crude benzene takes off the pyridine refining method schematic flow sheet.Number among the figure:
1 coking crude benzene: 2 denitrification refining agent: 3 sediments; 4 sediments; 5 take off pyridine benzene; Product behind 6 hydrogenation; 7 benzene,toluene,xylene products.
A: take off heavies column; B: static mixer; C, D: electrofining slurry tank or slurry tank; E: interchanger; F: hydrofining system; G: benzaldehyde product separation system.
Fig. 2 is the process flow diagram of reference example.Number among the figure:
The I coking crude benzene; Product behind the II hydrogenation; III benzene,toluene,xylene product.
X: take off heavies column; Y: hydrofining system; Z: benzaldehyde product separation system.
Embodiment
The present invention implements like this: coking crude benzene 1 through the light benzene heat exchange of taking off heavies column A and obtaining to normal temperature～78 ℃ with take off pyridine refining agent 2 and in (B), mix.This takes off pyridine compounds and their can be the denitrfying agent that ZL94115190.5 provides with agent, but is not limited to this denitrfying agent, can be existing denitrfying agent, and they are acid but do not comprise sulfuric acid, or the mixture of acid.Can be down to 1-20ppm by the basic nitrogen compound that takes off the crude benzol after pyridine compounds and their is handled.Taking off pyridine compounds and their is the 0.2%-5% of raw material with the adding weight percent of agent; Mixing temperature is 20-80 ℃. mixed crude benzol enters electrofining slurry tank (C) or/and slurry tank (D) carries out settlement separate; Separating tank comes out take off the pyridine compounds and their crude benzol and enter well heater (E) again and be heated to 60～500 ℃ after, enter (F) and carry out the hydrofining processing, the catalyzer that adopts be existing hydrogen addition technology use with Co-Mo catalyzer or the improved hydrogenation catalyst of molecular sieve as carrier, hydrogenation pressure is 0.5Mpa～21Mpa, and air speed is 0.1h
-1～15h
-1, the coking benzene after the hydrofining enters benzaldehyde product separation system (G) can obtain the benzene,toluene,xylene product.
The present invention is described in further detail below in conjunction with embodiment.But this should be interpreted as that the above-mentioned theme of the present invention only limits to following embodiment.
Reference example: referring to Fig. 2, take off heavies column (X) and take off heavy back crude benzol and directly enter hydrogenation system (Y), hydrogenation catalyst is to be the Co-Mo catalyzer (down with) of carrier with the molecular sieve, 380 ℃ of hydrogenation temperatures, pressure 3.0Mpa, air speed 2h-1, hydrogen-oil ratio 550: 1 can obtain qualified product by benzene knockout tower (Z) behind the hydrogenation, in the product refining benzene that obtains, benzene content is 99.9%, and sulphur content is 0.93ppm, and nitrogen content is 5ppm.
Embodiment 1: referring to Fig. 1, take off denitrfying agent that light benzene heat exchange after heavy provides with 2% ZL94115190.5 to normal temperature～78 ℃ and take off pyridine as taking off pyridine agent (down with), pyridine content is down to 12mg/kg from 3684 μ g/g, acid number is 0.05mgKOH/g, the crude benzol that takes off behind the pyridine enters hydrogenation system again after settlement separate, hydrogenation catalyst is to be the Co-Mo catalyzer (down with) of carrier with the molecular sieve, the processing condition of hydrogenation: 380 ℃ of temperature, pressure 3.0Mpa, air speed 2h
-1, hydrogen-oil ratio 550: 1, refining crude benzol enters the benzene separation system and obtains benzene,toluene,xylene, and benzene content is 99.93%, and sulphur content is 0.49ppm, and nitrogen content is 1ppm.
Embodiment 2: the crude benzol that takes off after heavy takes off pyridine with the pyridine agent of taking off that 2% ZL94115190.5 provides, pyridine content is down to 12mg/kg from 3684 μ g/g, acid number is 0.05mgKOH/g, the crude benzol that takes off behind the pyridine enters hydrogenation system again after settlement separate, hydrogenation catalyst is to be the Co-Mo catalyzer of carrier with the molecular sieve, 380 ℃ of hydrogenation temperatures, pressure 3.0Mpa, air speed 2.8h
-1, hydrogen-oil ratio 550: 1, in the product refining benzene that obtains, benzene content is 99.9%, and sulphur content is 0.86ppm, and nitrogen content is 2.6ppm.
Embodiment 3: the crude benzol that takes off after heavy takes off pyridine with the pyridine agent of taking off that 2% ZL94115190.5 provides, pyridine content is down to 12mg/kg from 3684 μ g/g, acid number is 0.05mgKOH/g, the crude benzol that takes off behind the pyridine enters hydrogenation system again after settlement separate, hydrogenation catalyst is to be the Co-Mo catalyzer of carrier with the molecular sieve, 369.2 ℃ of hydrogenation temperatures, pressure 3.0Mpa, air speed 2h
-1, hydrogen-oil ratio 550: 1, in the product refining benzene that obtains, benzene content is 99.9%, and sulphur content is 0.91ppm, and nitrogen content is 2.3ppm.
Embodiment 4: the crude benzol that takes off after heavy takes off pyridine with the pyridine agent of taking off that 2% ZL94115190.5 provides, pyridine content is down to 12mg/kg from 3684 μ g/g, acid number is 0.05mgKOH/g, the crude benzol that takes off behind the pyridine enters hydrogenation system again after settlement separate, hydrogenation catalyst is to be the Co-Mo catalyzer of carrier with the molecular sieve, 380 ℃ of hydrogenation temperatures, pressure 2.7Mpa, air speed 2h
-1, hydrogen-oil ratio 550: 1, in the product refining benzene that obtains, benzene content is 99.9%, and sulphur content is 0.89ppm, and nitrogen content is 2.1ppm.
If no special instructions, all percentage ratio is weight percentage among the present invention.
Claims (5)
1. one kind is raw material with the coal tar crude benzol, by taking off the refining combination process that carries out the hydrofining processing again of pyridine compounds and their, it is characterized in that coking crude benzene (1) is removed heavy benzol in taking off heavies column (A), the light benzene heat exchange enters electrofining slurry tank (C) pyridine compounds and their carries out hybrid reaction with agent (2) in static mixer (B) after or/and the middle sedimentation of natural subsidence (D) divides slag with taking off to normal temperature～78 ℃, sediment (3) (4) from slurry tank (C) or/and (D) bottom discharge, take off pyridine benzene (5) after interchanger (E) heat exchange to 60～500 ℃, enter hydrofining system (F) and carry out hydrogenation, product behind the hydrogenation (6) is through cooling, after the separation, the liquid benzene that obtains enters in the benzene separation system (G), obtains product purification benzene, toluene, dimethylbenzene (7); The described pyridine compounds and their that takes off with agent (2) is: be made up of A acidizer, B complexing agent and C solvent, A is the mixture that acidizer is selected from metaphosphoric acid, ortho-phosphoric acid, tetra-sodium, diacetyl oxide, pyromellitic acid anhydride or any two kinds of components; B is the mixture that complexing agent is selected from thiophosphoric anhydride, phosphorus trioxide, six tetraphosphine oxides, Vanadium Pentoxide in FLAKES or any two kinds of components; C is the mixture that solvent is selected from water, ethanol or any two kinds of components; Three kinds of shared ratios of component are: A is 6-85%(wt), B is that 0.1-85% (wt) and C are 0.1-85%(wt).
2. method according to claim 1 is characterized in that: taking off pyridine compounds and their is 0.2%-5% with the adding weight percent of agent (2).
3. method according to claim 1, be further characterized in that: slurry tank (C) and order (D) can be exchanged.
4. method according to claim 1, it is characterized in that: the electrofining strength of electric field in the electric slurry tank (C) is in 0-2000 volt/cm 2 scopes.
5. method according to claim 1, be further characterized in that: taking off the pyridine compounds and their unit can be also can be after taking off heavy constituent before the coal tar crude benzol takes off heavy constituent.
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| CN 201010574518 CN102030603B (en) | 2010-12-06 | 2010-12-06 | Process for carrying out pyridine removal and hydrogenating on coking crude benzol |
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| CN 201010574518 CN102030603B (en) | 2010-12-06 | 2010-12-06 | Process for carrying out pyridine removal and hydrogenating on coking crude benzol |
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| CN102030603A CN102030603A (en) | 2011-04-27 |
| CN102030603B true CN102030603B (en) | 2013-08-14 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101486623A (en) * | 2008-01-18 | 2009-07-22 | 沈和平 | Hydrofinishing method for crude benzol |
| CN101747130A (en) * | 2008-12-11 | 2010-06-23 | 上海宝钢化工有限公司 | Refining method of coking benzene product containing nitrogen impurities |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101486623A (en) * | 2008-01-18 | 2009-07-22 | 沈和平 | Hydrofinishing method for crude benzol |
| CN101747130A (en) * | 2008-12-11 | 2010-06-23 | 上海宝钢化工有限公司 | Refining method of coking benzene product containing nitrogen impurities |
Non-Patent Citations (4)
| Title |
|---|
| 江大好等人.焦化粗苯的组成及其加氢精制工艺技术的开发.《现代化工》.2009,第29卷(第5期),第72-77页. |
| 焦化粗苯加氢技术的发展与展望;赵守全等人;《燃料与化工》;20071101;第38卷(第6期);第43-45页 * |
| 焦化粗苯的组成及其加氢精制工艺技术的开发;江大好等人;《现代化工》;200905;第29卷(第5期);第72-77页 * |
| 赵守全等人.焦化粗苯加氢技术的发展与展望.《燃料与化工》.2007,第38卷(第6期),第43-45页. |
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