CN102766007A - Device and method for coked crude benzene full-fraction hydrofining and catalyst - Google Patents
Device and method for coked crude benzene full-fraction hydrofining and catalyst Download PDFInfo
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Abstract
The invention relates to a device and a method for full-fraction hydrofining of coked crude benzene which is a byproduct of the coal coking process and a catalyst. Two hydrogenation techniques of high-pressure and low-temperature liquid-phase hydrogenation and medium-pressure and medium-temperature gas-phase hydrogenation are adopted to achieve full-fraction hydrofining of crude benzene, hydrogenation raw materials are enriched, and economic benefit of the device is improved. The device and the method are characterized in that hydrogenated crude benzene is full-fraction and does not need to remove heavy components in advance. In order to prevent plugging of the device caused by polymerization of easily polymerizing materials at high temperature, the process of liquid-phase hydrogenation in the first section and gas-phase hydrogenation in the second section is adopted, and devices such as a first-section liquid-phase hydrogenation reactor, a second-section gas-phase hydrogenation reactor, a conveying pump, a compressor, a high-pressure flash drum and a related heat exchanger are adopted. By aid of the device, the method and the catalyst, heavy benzene removal before processing is avoided, energy consumption is reduced, raw material sources are increased, and heavy benzene by-products are prevented from being generated.
Description
Technical field
The invention belongs to coal chemical technology, be specifically related to coking crude benzene hydrogenation of total effluent refining plant, method and the catalyzer of coal tar process by-product.
Background technology
Coking crude benzene is the by product of coal tar process, obtains through washing oil washing coal gas, is about 1% of coke output.Coking crude benzene mainly contains triphen class material: benzene 65%, toluene 15.6%, YLENE and ethylbenzene 5%; Different polymkeric substance: cyclopentadiene 0.9%, vinylbenzene 2.5%, indenes 2.5%, coumarone 0.9%; High boiling substance: naphthalene 2.6%, methylnaphthalene 0.7%; Sulfur-nitrogen compound: thiophene, mercaptan and pyridine quinoline etc.In order to obtain highly purified benzene, toluene and YLENE product, need remove alkane, sulphur nitrogen class material in the crude benzol.
The traditional method of coked crude benzene refining is an acid wash; Because its production product gas purity does not reach the quality of grade oil aromatic hydrocarbon product and pollutes; Substituted by unifining gradually at present, hydrofining coking crude benzene has become prevailing working method.Hydrogenation technique has the KK method that adopts high temperature, highly compressed litol method and middle temperature, middle pressure, and wherein the working pressure of litol method is 6.0MPa, and service temperature is 600 ℃, and with the dealkylation of toluene and YLENE, product is single purified petroleum benzin.Press and moderate temperature hydrogenation technology during the KK method adopts, working pressure is 3.5MPa, 350 ℃ of service temperatures, and hydroconversion condition is gentle.These two kinds of hydrofinishing process all need carry out pre-treatment to raw material, remove easy resinification heavy benzols such as indenes, coumarone, avoid the coking in vaporizer of above-mentioned active substance, thereby only benzene, toluene and YLENE cut section are carried out unifining.
Heavy benzol generally accounts for the 6%-8% of crude benzol cut, but because of wherein containing sulphur, nitrogen compound, taste is heavy, and color is dark, and economic worth is low, is the by product of crude benzol processing enterprise, and price is lower than the crude benzol raw material.On the one hand, the fore-distillation of crude benzol has increased energy consumption, has reduced hydrogenating materials; In addition on the one hand, along with the over capacity of crude benzole hydrogenation device, occurred because of the nervous under-capacity operation that causes of raw material.Therefore, the full cut of crude benzol is carried out processing and refining, both can alleviate the deficiency of crude benzol raw material, can increase chemical productss such as C9 aromatic, naphthalene and methylnaphthalene again, improve the economic benefit of crude benzol processing enterprise.
Chinese patent CN102336622A discloses the retrieving arrangement and the separation method of crude benzole hydrogenation heavy constituent raffinates; Reclaim trimethylbenzene, indane, tetraline and naphthalene the heavy constituent behind hydrogenation; Increased crude benzole hydrogenation purified product; Help improving the economic benefit of device, but do not mention the hydrogenation process that contains heavy constituent in the patent.
Chinese patent CN102320910A discloses the method for the full cut of a kind of liquid phase one stage hydrofining crude benzol; With fresh hydrogen and crude benzol raw materials mix; Under the condition of the pressure of 4.0-7.0MPa and 320-340 ℃, react benzene,toluene,xylene that is purified and high boiling fraction.But this method adopts one-stage hydrogenation; Will certainly cause the temperature rise of reactor drum bigger, cause the difficulty of reactor design and manufacturing, though crude benzol has the hydrogenated oil of 60-80% to recycle when dissolving hydrogen; But when in tube furnace, being heated to more than 320 ℃, have the trend of coking.This method is provided with one and drives the hydrogenator that is equipped with, possibly be the countermeasure to the coking in the hydrogenator.
Crude benzol is carried out unifining constantly, if adopt two sections traditional gas phase hydrogenations, because of the existence of unsaturated materialss such as the vinylbenzene in the crude benzol, indenes and coumarone, polymerization in vaporizer easily causes the device fluctuation of service.Therefore, developing and a kind ofly can carry out unifining to full cut, can avoid polymeric novel process and catalyzer again, is necessary.
Summary of the invention
The object of the present invention is to provide a kind of novel crude benzol hydrogenation of total effluent flow process and catalyzer; Adopt high pressure, low temperature liquid phase hydrogenation and middle pressure, the middle wet two-stage hydrogenation technology that combines of hydrogenation mutually; Realization is to the unifining of the full cut of crude benzol; Enrich the raw material of hydrogenation, improve the economic benefit of device.
The principal feature of coking crude benzene hydrogenation of total effluent purification techniques of the present invention is that the crude benzol of hydrogenation is full cut, need not remove heavy constituent in advance.For fear of being prone to the obstruction that polymeric material polymerization at high temperature causes equipment; Adopt one section liquid-phase hydrogenatin and two sections gas phase hydrogenation process combined; Mainly comprise one section liquid phase hydrogenation reactor, two sections gas phase hydrogenation reaction devices, equipment such as transferpump, compressor, high pressure flash groove and relevant interchanger.
Coking crude benzene hydrogenation of total effluent refining plant of the present invention is following:
Make-up hydrogen compressor 1 is provided with the import of fresh hydrogen S1; The outlet of make-up hydrogen compressor 1 is connected to the top inlet of one-stage hydrogenation reactor drum 5; Crude benzol preheater 2 is provided with the inlet of the full cut S2 of crude benzol; The outlet of crude benzol preheater 2 is connected to the upper entrance of one-stage hydrogenation reactor drum 5; The outlet at bottom of one-stage hydrogenation reactor drum 5 is connected respectively to the inlet of one-stage hydrogenation reactor cycles pump 4 and the inlet of mixing tank 6, and the outlet of one-stage hydrogenation reactor cycles pump 4 is connected to the inlet of one-stage hydrogenation product water cooler 3, and the outlet of one-stage hydrogenation product water cooler 3 is connected to the upper entrance of one-stage hydrogenation reactor drum 5; The outlet of mixing tank 6 is connected to the tube side inlet of interchanger 7; The tube side outlet of interchanger 7 is connected to the top inlet of secondary hydrogenation reactor drum 9; The bottom of secondary hydrogenation reactor drum 9 is connected to the shell side inlet of interchanger 7; The shell side outlet of interchanger 7 is connected to the inlet of secondary hydrogenation product water cooler 8, and the outlet of secondary hydrogenation product water cooler 8 is connected to the inlet of hp flash drum 10; The top of hp flash drum 10 is connected to the inlet of circulating hydrogen compressor 11, bottom extraction hydrogenation products; The outlet of circulating hydrogen compressor 11 is connected to the top inlet of mixing tank 6.
Coking crude benzene hydrogenation of total effluent process for purification of the present invention is following:
Hydrogenation reaction takes place through the full cut S2 of crude benzol of compressor 1 back and process preheater 2 in fresh hydrogen S1 in one-stage hydrogenation reactor drum 5; An one-stage hydrogenation product part is sent into one-stage hydrogenation product water cooler 3 by impeller pump 6, and cooling back material returns one-stage hydrogenation reactor drum 5; A part is with after the recycle hydrogen that comes from circulating hydrogen compressor 11 mixes in vaporizer 8, and with the 9 product heat exchange of secondary hydrogenation reactor drum, entering secondary hydrogenation reactor drum 9 carries out secondary hydrogenation after the heat exchange in interchanger 7.The material that leaves secondary hydrogenation reactor drum 9 gets into secondary hydrogenation product water cooler 8 after interchanger 7 heat exchange.Cooled product gets into high pressure flash vessel 10, and by circulating hydrogen compressor 11 Returning reactors, the liquid phase discharging gets into follow-up stabilizer tower and monomer aromatic hydrocarbons refining system to gas phase as circulating hydrogen.
One section with the needed whole fresh hydrogen S1 of secondary hydrogenation after make-up hydrogen compressor 1 is compressed to predetermined pressure 6.0-8.0MPa, go into one-stage hydrogenation reactor drum 5; After interchanger 2 is preheating to 50-160 ℃, send into one-stage hydrogenation reactor drum 5 from the crude benzol S2 of high-speed pump, through liquid distributor back entering one-stage hydrogenation reactor drum 5 beds that distribute by high-speed pump; In this bed, carry out the hydrogenation reaction of alkene; Temperature of reaction is 50-160 ℃, and reaction pressure is 6.0-8.0MPa, and liquid air speed is 0.8-2.0hr
-1, hydrogen-oil ratio is 50-100:1, and components such as easy polymeric vinylbenzene, indenes and cyclopentadiene is saturated, generates ethylbenzene, indane and cyclopentenes or pentamethylene respectively.In order to prevent that the first stage reactor temperature is too high and to prevent the generation of polymkeric substance; One-stage hydrogenation reactor drum 5 a hydrogenation products part gets into vaporizer 6; A part is cooled to 50-160 ℃ through one-stage hydrogenation product water cooler 3; Return the charging of one-stage hydrogenation reactor drum 5, the hydrogenation products that wherein returns is 0-3:1 with the volume ratio ratio of one-stage hydrogenation charging.
One section reaction product is mixed in vaporizer 6 with the hydrogen that comes from circulating hydrogen compressor 11, and the control hydrogen-oil ratio is 300-1000:1, gets into interchanger 7 and the 9 product heat exchange of secondary hydrogenation reactor drum; Charging further is warmed up to 290-330 ℃; Get into secondary hydrogenation reactor drum 9, carry out the further saturated reaction of unsaturates, and the sulfur-bearing nitrogenous compound is carried out hydrogenation; Organosulfur is become inorganic sulfur, and organonitrogen becomes inorganic nitrogen.The hydrogen-oil ratio of secondary hydrogenation reactor drum is 300-1000:1, preferred 500-900:1, liquid air speed 0.6-1.2hr
-1Reaction pressure is 2.5-3.5MPa; The material that leaves secondary hydrogenation reactor drum 9 is cooled to 50-160 ℃ through secondary hydrogenation product water cooler and gets into high pressure flash vessel 10; Gas phase is returned mixing tank 6 as circulating hydrogen by circulating hydrogen compressor 11, and the liquid phase discharging gets into follow-up stabilizer tower and monomer aromatic hydrocarbons refining system.
The material that the present invention handles need not carry out pre-separation for directly coming from coking crude benzene, and all cut comprises that indenes, coumarone and a spot of naphthalene series substance matter all get into hydrogenation system.
The catalyzer that one-stage hydrogenation reactor drum of the present invention is adopted is loading type NiMo, NiW, NiMoW sulfide catalyst, and carrier is the oxide carrier with mesopore composite structure, and oxide carrier is SiO
2-Al
2O
3, TiO
2-Al
2O
3Or ZrO
2-Al
2O
3The catalyzer that the secondary hydrogenation reactor drum is adopted is load type Co Mo, CoW, CoMoW sulfide catalyst, and carrier is the composite oxide carrier with central hole structure, and oxide carrier is SiO
2-Al
2O
3, TiO
2-Al
2O
3Or ZrO
2-Al
2O
3
Wherein, the catalyzer of one-stage hydrogenation employing does not influence the catalyzer that secondary hydrogenation adopts.
The hydrogenation catalyst preparation method that the present invention uses is following: through the mineral compound of use Si, Ti or Zr or water or the globular of alcoholic solution dipping industry or the Al of cylinder or other shape of organic cpds
2O
3Carrier through 80-120 ℃ of dry 5-10 hour, prepared through 450-550 ℃ of roasting 3-6 hour again.
Adopt the equivalent impregnation legal system to be equipped with catalyzer, its concrete preparation method is (is example with loading type NiMo catalyzer) as follows: with nickelous nitrate and and ammonium molybdate mixing solutions impregnated carrier, after drying, roasting 2h under 550 high temperature.Roasting gets loading type NiMo catalyzer.Concentration or dipping number of times through control solution guarantee that the total amount of carrier loaded Ni of the every 100g of metal loading and W is 0.5-20g.The wet method sulfuration is a vulcanizing agent with the 3%CS2+97% hexanaphthene of 0.12ml/min, curing temperature 300 degree, hydrogen dividing potential drop 3MPa, hydrogen-oil ratio 12, curing time 8h.
CoMo, CoW, three kinds of Preparation of catalysts methods of CoMoW are identical with loading type NiMo catalyzer.Just precursor becomes Xiao Suangu, ammonium metawolframate and ammonium molybdate.The total amount of controlling the carrier loaded Co of every 100g and W and Mo is 0.5-20g.
The effect that the present invention reaches is: adopt one section liquid-phase hydrogenatin and two sections gas phase hydrogenation technologies and corresponding catalyzer; Can carry out hydrogenation to the whole cut of coking benzene; Suitable flow scheme design has been avoided the obstruction of easy polymeric materials such as indenes to reactor drum; Device smooth running continuously, all the crude benzol cut is processed as the product that no sulphur does not have nitrogen.
The present invention has compared following advantage with prior art:
1, the present invention is a processing object with the full cut of crude benzol, has avoided at first removing heavy benzol in first being processed, has reduced energy consumption, has increased raw material sources, and has avoided generation heavy benzol by product;
2, the flow process that adopted adopts one section liquid-phase hydrogenatin, and temperature of reaction 50-160 ℃, and the circulation of one-stage hydrogenation product is arranged, it is saturated to be prone to polymeric olefinic material hydrogenation, has avoided olefinic material polymerization at high temperature;
3, materials such as the indenes in the full cut of crude benzol, naphthalene can be generated indane by hydrogenation; Material such as naphthane and perhydronaphthalene; The coumarone hydrogenation deoxidation generates o-methylethylbenzene, and both can further purify is fine chemicals, also can be used as C9 aromatic solvent naphtha or clean fuel products and sells.
Description of drawings
Fig. 1 is a schematic flow sheet of the present invention.
S1, fresh hydrogen; S2, the full cut of crude benzol; S3, hydrogenation products; 1, make-up hydrogen compressor; 2, preheater; 3, one-stage hydrogenation product water cooler; 4, one-stage hydrogenation reactor cycles pump; 5, the one-stage hydrogenation reactor drum; 6, mixing tank; 7, interchanger; 8, secondary hydrogenation product water cooler; 9, the secondary hydrogenation reactor drum; 10, hp flash drum; 11, circulating hydrogen compressor.
Specific embodiments
To combine the accompanying drawing specific embodiments of the invention to be described in further detail below.
Catalyst carrier for hydrgenating adopts composite oxide carrier SiO
2-Al
2O
3, TiO
2-Al
2O
3And ZrO
2-Al
2O
3, be through the mineral compound of use Si, Ti or Zr or water or the globular of alcoholic solution dipping industry or the Al of cylinder or other shape of organic cpds
2O
3Carrier through 80-120 ℃ of dry 5-10 hour, prepared through 450-550 ℃ of roasting 3-6 hour again.
The catalyzer that one-stage hydrogenation reactor drum of the present invention is adopted is loading type NiMo, NiW, NiMoW sulfide catalyst, and carrier is the oxide carrier with mesopore composite structure, and oxide carrier is SiO
2-Al
2O
3, TiO
2-Al
2O
3Or ZrO
2-Al
2O
3
The catalyzer that secondary hydrogenation reactor drum of the present invention is adopted is load type Co Mo, CoW, CoMoW sulfide catalyst, and carrier is the composite oxide carrier with central hole structure, and oxide carrier is SiO
2-Al
2O
3, TiO
2-Al
2O
3Or ZrO
2-Al
2O
3
Wherein, the catalyzer of one-stage hydrogenation employing does not influence the catalyzer that secondary hydrogenation adopts.
Adopt the equivalent impregnation legal system to be equipped with catalyzer, its concrete preparation method is (is example with loading type NiMo catalyzer) as follows: with nickelous nitrate and and ammonium molybdate mixing solutions impregnated carrier, after drying, roasting 2h under 550 high temperature.Roasting gets loading type NiMo catalyzer.Concentration or dipping number of times through control solution guarantee that the total amount of carrier loaded Ni of the every 100g of metal loading and W is 0.5-20g.The wet method sulfuration is a vulcanizing agent with the 3%CS2+97% hexanaphthene of 0.12ml/min, curing temperature 300 degree, hydrogen dividing potential drop 3MPa, hydrogen-oil ratio 12, curing time 8h.
CoMo, CoW, three kinds of Preparation of catalysts methods of CoMoW are identical with loading type NiMo catalyzer.Just precursor becomes Xiao Suangu, ammonium metawolframate and ammonium molybdate.The total amount of controlling the carrier loaded Co of every 100g and W and Mo is 0.5-20g.
The full cut S2 of crude benzol boiling range is 75-195 ℃; The feed hydrogen oil ratio of the full cut S2 of fresh hydrogen S1 and crude benzol is 60:1, after make-up hydrogen compressor 1 is compressed to predetermined pressure 8.0MPa, goes into one-stage hydrogenation reactor drum 5, from the full cut S2 of crude benzol of high-speed pump after interchanger 2 is preheating to 100 ℃; Send into one-stage hydrogenation reactor drum 5 by high-speed pump; After liquid distributor distributes, get into the first stage reactor bed, in this bed, carry out the hydrogenation reaction of alkene, temperature of reaction is 100-120 ℃; Reaction pressure is 6.0MPa, and liquid air speed is 1hr
-1, hydrogen-oil ratio is 60:1, and components such as easy polymeric vinylbenzene, indenes and cyclopentadiene is saturated, generates ethylbenzene, indane and cyclopentenes or pentamethylene respectively.In order to prevent that the first stage reactor temperature is too high and to prevent the generation of polymkeric substance; One-stage hydrogenation reactor drum 5 a hydrogenation products part gets into vaporizer 6; A part is cooled to 55 ℃ through one-stage hydrogenation product water cooler 3; Return the charging of one-stage hydrogenation reactor drum 5, the hydrogenation products that wherein returns is 1:1 with the volume ratio ratio of one-stage hydrogenation charging.In the one-stage hydrogenation reaction, the catalyzer of employing is a loading type NiMo sulfide catalyst, and carrier is the oxide carrier with mesopore composite structure, and oxide carrier is SiO
2-Al
2O
3
One section reaction product is mixed in vaporizer 6 with the circulating hydrogen that comes from circulating hydrogen compressor 11, and the control hydrogen to oil volume ratio is 800:1, gets into interchanger 7 and the 9 product heat exchange of secondary hydrogenation reactor drum; Charging further is warmed up to 290 ℃; Get into secondary hydrogenation reactor drum 9, carry out the further saturated reaction of unsaturates, and the sulfur-bearing nitrogenous compound is carried out hydrogenation; Organosulfur is become inorganic sulfur, and organonitrogen becomes inorganic nitrogen.The hydrogen-oil ratio of secondary hydrogenation reactor drum 9 is 800:1, liquid air speed 0.6hr
-1, reaction pressure is 2.5MPa, and the material that leaves second stage reactor 9 gets into high pressure flash vessel 10 after being cooled to 55 ℃, and by circulating hydrogen compressor 11 Returning evaporimeters 6, the liquid phase discharging gets into follow-up stabilizer tower and monomer aromatic hydrocarbons refining system to gas phase as circulating hydrogen.The catalyzer that adopts in the secondary hydrogenation reaction is a load type Co Mo sulfide catalyst, and carrier is the composite oxide carrier with central hole structure, and oxide carrier is SiO
2-Al
2O
3
Product index is:
| Name of product | Leading indicator |
| Sulphur content | 0.5ppm |
| Nitrogen content | 0.2ppm |
| The aromatic hydrocarbons retention rate | 99.5% |
The full cut S2 of crude benzol boiling range is 77-200 ℃; The feed hydrogen oil ratio of the full cut S2 of fresh hydrogen S1 and crude benzol is 80:1, after make-up hydrogen compressor 1 is compressed to predetermined pressure 7.0MPa, goes into one-stage hydrogenation reactor drum 5, from the full cut S2 of crude benzol of high-speed pump after interchanger 2 is preheating to 100 ℃; Send into one-stage hydrogenation reactor drum 5 by high-speed pump; After liquid distributor distributes, get into the first stage reactor bed, in this bed, carry out the hydrogenation reaction of alkene, temperature of reaction is 110-130 ℃; Reaction pressure is 7.0MPa, and liquid air speed is 1.5hr
-1, components such as easy polymeric vinylbenzene, indenes and cyclopentadiene is saturated, generate ethylbenzene, indane and cyclopentenes or pentamethylene respectively.In order to prevent that the first stage reactor temperature is too high and to prevent the generation of polymkeric substance; One-stage hydrogenation reactor drum 5 a hydrogenation products part gets into vaporizer 6; A part is cooled to 85 ℃ through one-stage hydrogenation product water cooler 3; Return the charging of one-stage hydrogenation reactor drum 5, the hydrogenation products that wherein returns is 2:1 with the volume ratio ratio of one-stage hydrogenation charging.In the one-stage hydrogenation reaction, the catalyzer of employing is a loading type NiW sulfide catalyst, and carrier is the oxide carrier with mesopore composite structure, and oxide carrier is TiO
2-Al
2O
3
One section reaction product is mixed in vaporizer 6 with the hydrogen that comes from circulating hydrogen compressor 11, and the control hydrogen to oil volume ratio is 800:1, gets into interchanger 7 and the 9 product heat exchange of secondary hydrogenation reactor drum; Charging further is warmed up to 300 ℃; Get into secondary hydrogenation reactor drum 9, carry out the further saturated reaction of unsaturates, and the sulfur-bearing nitrogenous compound is carried out hydrogenation; Organosulfur is become inorganic sulfur, and organonitrogen becomes inorganic nitrogen.The hydrogen-oil ratio of secondary hydrogenation reactor drum is 900:1, liquid air speed 1hr
-1, reaction pressure is 3MPa, and the material that leaves second stage reactor 9 gets into high pressure flash vessel 12 after being cooled to 85 ℃, and by circulating hydrogen compressor Returning evaporimeter 6, the liquid phase discharging gets into follow-up stabilizer tower and monomer aromatic hydrocarbons refining system to gas phase as circulating hydrogen.The catalyzer that adopts in the secondary hydrogenation reaction is a load type Co W sulfide catalyst, and carrier is the composite oxide carrier with central hole structure, and oxide carrier is TiO
2-Al
2O
3
Product index is:
| Name of product | Leading indicator |
| Sulphur content | 0.3ppm |
| Nitrogen content | 0.1ppm |
| The aromatic hydrocarbons retention rate | 99.1% |
The full cut S2 of crude benzol boiling range is 77-200 ℃; The feed hydrogen oil ratio of the full cut S2 of fresh hydrogen S1 and crude benzol is 100:1, after make-up hydrogen compressor 1 is compressed to predetermined pressure 8.0MPa, goes into one-stage hydrogenation reactor drum 5, from the full cut S2 of crude benzol of high-speed pump after interchanger 2 is preheating to 100 ℃; Send into one-stage hydrogenation reactor drum 5 by high-speed pump; After liquid distributor distributes, get into the first stage reactor bed, in this bed, carry out the hydrogenation reaction of alkene, temperature of reaction is 120-140 ℃; Reaction pressure is 8.0MPa, and liquid air speed is 2hr
-1, components such as easy polymeric vinylbenzene, indenes and cyclopentadiene is saturated, generate ethylbenzene, indane and cyclopentenes or pentamethylene respectively.In order to prevent that the first stage reactor temperature is too high and to prevent the generation of polymkeric substance; One-stage hydrogenation reactor drum 5 a hydrogenation products part gets into vaporizer 6; A part is cooled to 120 ℃ through one-stage hydrogenation product water cooler 3; Return the charging of one-stage hydrogenation reactor drum 5, the hydrogenation products that wherein returns is 3:1 with the volume ratio ratio of one-stage hydrogenation charging.In the one-stage hydrogenation reaction, the catalyzer of employing is a loading type NiMoW sulfide catalyst, and carrier is the oxide carrier with mesopore composite structure, and oxide carrier is ZrO
2-Al
2O
3
One section reaction product is mixed in vaporizer 6 with the hydrogen that comes from circulating hydrogen compressor 11, and the control hydrogen to oil volume ratio is 800:1, gets into interchanger 7 and the 9 product heat exchange of secondary hydrogenation reactor drum; Charging further is warmed up to 310 ℃; Get into secondary hydrogenation reactor drum 9, carry out the further saturated reaction of unsaturates, and the sulfur-bearing nitrogenous compound is carried out hydrogenation; Organosulfur is become inorganic sulfur, and organonitrogen becomes inorganic nitrogen.The hydrogen-oil ratio of secondary hydrogenation reactor drum is 1000:1, liquid air speed 1.2hr
-1, reaction pressure is 3.5MPa, and the material that leaves second stage reactor 9 gets into high pressure flash vessel 12 after being cooled to 120 ℃, and by circulating hydrogen compressor Returning evaporimeter 6, the liquid phase discharging gets into follow-up stabilizer tower and monomer aromatic hydrocarbons refining system to gas phase as circulating hydrogen.The catalyzer that adopts in the secondary hydrogenation reaction is a load type Co MoW sulfide catalyst, and carrier is the composite oxide carrier with central hole structure, and oxide carrier is ZrO
2-Al
2O
3
Product index is:
| Name of product | Leading indicator |
| Sulphur content | 0.5ppm |
| Nitrogen content | 0.2ppm |
| The aromatic hydrocarbons retention rate | 99% |
Claims (6)
1. coking crude benzene hydrogenation of total effluent refining plant; It is characterized in that make-up hydrogen compressor 1 is provided with the import of fresh hydrogen S 1; The outlet of make-up hydrogen compressor 1 is connected to the top inlet of one-stage hydrogenation reactor drum 5; Crude benzol preheater 2 is provided with the inlet of the full cut S2 of crude benzol; The outlet of crude benzol preheater 2 is connected to the upper entrance of one-stage hydrogenation reactor drum 5; The outlet at bottom of one-stage hydrogenation reactor drum 5 is connected respectively to the inlet of one-stage hydrogenation reactor cycles pump 4 and the inlet of mixing tank 6, and the outlet of one-stage hydrogenation reactor cycles pump 4 is connected to the inlet of one-stage hydrogenation product water cooler 3, and the outlet of one-stage hydrogenation product water cooler 3 is connected to the upper entrance of one-stage hydrogenation reactor drum 5; The outlet of mixing tank 6 is connected to the tube side inlet of interchanger 7; The tube side outlet of interchanger 7 is connected to the top inlet of secondary hydrogenation reactor drum 9; The bottom of secondary hydrogenation reactor drum 9 is connected to the shell side inlet of interchanger 7; The shell side outlet of interchanger 7 is connected to the inlet of secondary hydrogenation product water cooler 8, and the outlet of secondary hydrogenation product water cooler 8 is connected to the inlet of hp flash drum 10; The top of hp flash drum 10 is connected to the inlet of circulating hydrogen compressor 11, bottom extraction hydrogenation products; The outlet of circulating hydrogen compressor 11 is connected to the top inlet of mixing tank 6.
2. the coking crude benzene hydrogenation of total effluent process for purification of claim 1; It is characterized in that fresh hydrogen S1 in one-stage hydrogenation reactor drum 5 hydrogenation reaction takes place through the full cut S2 of crude benzol of compressor 1 back and process preheater 2; An one-stage hydrogenation product part is sent into one-stage hydrogenation product water cooler 3 by impeller pump 6, and cooling back material returns one-stage hydrogenation reactor drum 5; A part is with after the recycle hydrogen that comes from circulating hydrogen compressor 11 mixes in vaporizer 8, and with the 9 product heat exchange of secondary hydrogenation reactor drum, entering secondary hydrogenation reactor drum 9 carries out secondary hydrogenation after the heat exchange in interchanger 7; The material that leaves secondary hydrogenation reactor drum 9 gets into secondary hydrogenation product water cooler 8 after interchanger 7 heat exchange; Cooled product gets into high pressure flash vessel 10, and by circulating hydrogen compressor 11 Returning reactors, the liquid phase discharging gets into follow-up stabilizer tower and monomer aromatic hydrocarbons refining system to gas phase as circulating hydrogen.
3. method as claimed in claim 2; It is characterized in that one section with the needed whole fresh hydrogen S1 of secondary hydrogenation after make-up hydrogen compressor 1 is compressed to predetermined pressure 6.0-8.0MPa, get into one-stage hydrogenation reactor drum 5; After interchanger 2 is preheating to 50-160 ℃, send into one-stage hydrogenation reactor drum 5 from the crude benzol S2 of high-speed pump, through liquid distributor back entering one-stage hydrogenation reactor drum 5 beds that distribute by high-speed pump; In this bed, carry out the hydrogenation reaction of alkene; Temperature of reaction is 50-160 ℃, and reaction pressure is 6.0-8.0MPa, and liquid air speed is 0.8-2.0hr
-1, hydrogen-oil ratio is 50-100:1; One-stage hydrogenation reactor drum 5 a hydrogenation products part gets into vaporizer 6; A part is cooled to 50-160 ℃ through one-stage hydrogenation product water cooler 3; Return the charging of one-stage hydrogenation reactor drum 5, the hydrogenation products that wherein returns is 0-3:1 with the volume ratio ratio of one-stage hydrogenation charging.
4. method as claimed in claim 2; It is characterized in that one section reaction product mixes in vaporizer 6 with the hydrogen that comes from circulating hydrogen compressor 11; The control hydrogen-oil ratio is 300-1000:1; Get into interchanger 7 and the 9 product heat exchange of secondary hydrogenation reactor drum, charging further is warmed up to 290-330 ℃, get into secondary hydrogenation reactor drum 9; The hydrogen-oil ratio of secondary hydrogenation reactor drum is 300-1000:1, liquid air speed 0.6-1.2hr
-1Reaction pressure is 2.5-3.5MPa; The material that leaves secondary hydrogenation reactor drum 9 is cooled to 50-160 ℃ through secondary hydrogenation product water cooler and gets into high pressure flash vessel 10; Gas phase is returned mixing tank 6 as circulating hydrogen by circulating hydrogen compressor 11, and the liquid phase discharging gets into follow-up stabilizer tower and monomer aromatic hydrocarbons refining system.
5. a coking crude benzene hydrogenation of total effluent catalyst for refining is characterized in that the catalyzer that the one-stage hydrogenation reactor drum is adopted is loading type NiMo, NiW, NiMoW sulfide catalyst, and carrier is the oxide carrier with mesopore composite structure, and oxide carrier is SiO
2-Al
2O
3, TiO
2-Al
2O
3Or Zr
O2-Al
2O
3The catalyzer that the secondary hydrogenation reactor drum is adopted is load type Co Mo, CoW, CoMoW sulfide catalyst, and carrier is the composite oxide carrier with central hole structure, and oxide carrier is SiO
2-Al
2O
3, TiO
2-Al
2O
3Or ZrO
2-Al
2O
3
6. described catalyzer as claimed in claim 5 is characterized in that through the mineral compound of use Si, Ti or Zr or water or the globular of alcoholic solution dipping industry or the Al of cylinder or other shape of organic cpds
2O
3Carrier through 80-120 ℃ of dry 5-10 hour, prepared through 450-550 ℃ of roasting 3-6 hour again.
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| CN103120943A (en) * | 2013-01-29 | 2013-05-29 | 沈阳三聚凯特催化剂有限公司 | Application of Mo-Ni catalyst in hydrogenation of mixture of crude benzene and absorber oil |
| CN103274885A (en) * | 2013-06-08 | 2013-09-04 | 四川省煤焦化集团有限公司 | Crude benzene hydrorefining process |
| CN104371761A (en) * | 2014-10-15 | 2015-02-25 | 上海建安化工设计有限公司 | Heavy benzene hydrogenation upgrading process |
| CN108003929A (en) * | 2017-12-18 | 2018-05-08 | 金冬梅 | A kind of heavy benzene hydrogenation process for refining |
| CN108485703A (en) * | 2018-04-11 | 2018-09-04 | 金冬梅 | A kind of heavy benzene hydrogenation process for purification |
| CN109651051A (en) * | 2019-01-14 | 2019-04-19 | 武汉聚川科技有限公司 | A kind of crude benzol catalytic hydrogenation process and equipment |
| CN110872209A (en) * | 2018-08-30 | 2020-03-10 | 中国石化工程建设有限公司 | Device and method for preparing phenethyl alcohol by acetophenone hydrogenation |
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| CN103120943A (en) * | 2013-01-29 | 2013-05-29 | 沈阳三聚凯特催化剂有限公司 | Application of Mo-Ni catalyst in hydrogenation of mixture of crude benzene and absorber oil |
| CN103122260B (en) * | 2013-01-29 | 2015-06-03 | 沈阳三聚凯特催化剂有限公司 | Hydrofining technique of mixture of heavy benzene and absorber oil |
| CN103122260A (en) * | 2013-01-29 | 2013-05-29 | 沈阳三聚凯特催化剂有限公司 | Hydrofining technique of mixture of heavy benzene and absorber oil |
| CN103274885A (en) * | 2013-06-08 | 2013-09-04 | 四川省煤焦化集团有限公司 | Crude benzene hydrorefining process |
| CN103274885B (en) * | 2013-06-08 | 2015-12-23 | 四川省煤焦化集团有限公司 | Crude benzole hydrogenation process for refining |
| CN104371761A (en) * | 2014-10-15 | 2015-02-25 | 上海建安化工设计有限公司 | Heavy benzene hydrogenation upgrading process |
| CN108003929A (en) * | 2017-12-18 | 2018-05-08 | 金冬梅 | A kind of heavy benzene hydrogenation process for refining |
| CN108485703A (en) * | 2018-04-11 | 2018-09-04 | 金冬梅 | A kind of heavy benzene hydrogenation process for purification |
| CN110872209A (en) * | 2018-08-30 | 2020-03-10 | 中国石化工程建设有限公司 | Device and method for preparing phenethyl alcohol by acetophenone hydrogenation |
| CN109651051A (en) * | 2019-01-14 | 2019-04-19 | 武汉聚川科技有限公司 | A kind of crude benzol catalytic hydrogenation process and equipment |
| CN113492012A (en) * | 2020-04-03 | 2021-10-12 | 中国石油化工股份有限公司 | Non-noble metal Ni-based catalyst and preparation method thereof, and method for preparing cyclopentane by cyclopentadiene hydrogenation |
| CN113492012B (en) * | 2020-04-03 | 2024-06-11 | 中国石油化工股份有限公司 | Non-noble metal Ni-based catalyst, preparation method thereof and method for preparing cyclopentane by cyclopentadiene hydrogenation |
| CN111939584A (en) * | 2020-09-04 | 2020-11-17 | 中冶焦耐(大连)工程技术有限公司 | Process and system for evaporating crude benzene in benzene hydrogenation reaction system |
| CN111939584B (en) * | 2020-09-04 | 2023-09-15 | 中冶焦耐(大连)工程技术有限公司 | Crude benzene evaporation process and system in benzene hydrogenation reaction system |
| CN112500257A (en) * | 2020-12-18 | 2021-03-16 | 武汉科林化工集团有限公司 | Process for extracting cyclopentane by hydrofining crude benzene containing dicyclopentadiene |
| CN112500257B (en) * | 2020-12-18 | 2022-05-17 | 武汉科林化工集团有限公司 | Process for extracting cyclopentane by hydrofining crude benzene containing dicyclopentadiene |
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