CN100594966C - Method for preparing hydrogen and nitrogen by catalytic cracking regenerative fume - Google Patents

Method for preparing hydrogen and nitrogen by catalytic cracking regenerative fume Download PDF

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CN100594966C
CN100594966C CN200710017069A CN200710017069A CN100594966C CN 100594966 C CN100594966 C CN 100594966C CN 200710017069 A CN200710017069 A CN 200710017069A CN 200710017069 A CN200710017069 A CN 200710017069A CN 100594966 C CN100594966 C CN 100594966C
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regenerator
temperature
gas
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catalyst
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CN101143289A (en
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高玉玲
何燕文
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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Abstract

The invention relates to a method of producing hydrogen and nitrogen by catalytic cracking of stack gas. The invention has main content that: the high temperature oxygen-contained gas of a second regenerator enters to the bottom of a first regenerator, and is contacted, heated and burnt with a mixing catalyst composed of a carbon deposition catalyst in a self stripper and a regenerant in the second regenerator. The regenerating gas on the upper part of the first regenerator is separated from a half-regenerant by a cyclone separator. The generating gas enters into a pressure energy recovery system, and then enters into the subsequent hydrogen and nitrogen producing process. The half-regenerant enters into the second regenerator through a dipleg, and then is contacted and burnt with full burnt prevailing wind. The stripped carbon deposition catalyst returns to the first regenerator, and then a circulating is formed, in order to effectively use CO and CO2 in the regenerating gas and CO2 produced in the subsequent CO intermediate temperature changing process, and to improve the ratio of the carbon deposition on the first regenerator catalyst transferring into CO, and furthermore to improve the unit carbon deposition hydrogen yield rate of the catalyst.

Description

Regeneration fume from catalytic cracking prepares the method for hydrogen and nitrogen
Technical field
The process that the present invention relates to new catalytic cracking reaction-regeneration techniques and utilize its regenerated flue gas hydrogen manufacturing, system nitrogen, more particularly, being a kind of technology that existing apparatus improves power of regeneration and improves yield of light oil that is suitable for, is a kind of technology that reduces greenhouse gas emission and obtain a large amount of cheap hydrogen.
Background technology
As everyone knows, in order to improve the quality of gasoline, diesel oil, hydrofinishing has become a kind of requisite secondary operations means, how to obtain the cheap hydrogen source of q.s, is a difficult problem of puzzlement oil refining industry.
CN1400159A has proposed a kind of method of utilizing regeneration fume from catalytic cracking hydrogen manufacturing, though it is different from the higher ways of hydrogen cost such as methane steam cracking hydrogen manufacturing commonly used at present, heavy oil hydrogen manufacturing, coal hydrogen manufacturing, but, because the catalyst and the oxygen-containing gas of the carbon distribution in its first regenerator react under 500～660 ℃ of conditions, temperature is lower, and first regenerator and second regenerator be air intake respectively, the high-temperature flue gas that second regenerator is produced road discharging in addition, not only the pressure of flue gas can not get abundant recovery, and second regenerator produces the CO in the flue gas 2And the CO that the temperature conversion is produced among the follow-up CO 2Can not get effective utilization, that is to say, the ratio that the carbon distribution in first regenerator on the catalyst is converted into CO is not high, is restricted thereby make catalyst unit's carbon distribution produce the hydrogen rate.
Now, many oil refining enterprises are arranged, and there are the following problems: not only catalytic cracking unit regenerator coke-burning capacity is not enough, is badly in need of improving, and also needs to build device for producing hydrogen, how to spend a spot of fund to satisfy this two difficult problems simultaneously?
Summary of the invention
The object of the present invention is to provide new regeneration fume from catalytic cracking to prepare the method for hydrogen and nitrogen, so that CO in the regenerated flue gas and CO 2And the CO that produced of follow-up CO middle temperature transformation 2Be utilized effectively, improve the ratio that the carbon distribution on the catalyst in first regenerator is converted into CO, produce the hydrogen rate thereby improve catalyst unit's carbon distribution.
The present invention is directed to existing different catalytic cracking process different technical schemes be provided respectively, be respectively:
The method that first kind of regeneration fume from catalytic cracking prepares hydrogen and nitrogen is:
(1) burning and enter the auxiliary oven that goes into operation after main air is forced into 0.3～0.45MPa, is that 670～760 ℃ high temperature half regenerative agent contacts, burns in second regenerator bottoms with temperature from the first regenerator cyclone separator group dipleg, from the CO of decarbonization system 2Enter the second regenerator middle and upper part through pipeline, enter the high-order storage tank of catalyst by the second regenerator top and realize separating of regeneration oxygen gas and regenerative agent; Temperature is that 660～780 ℃ regenerative agent to the feedstock oil of descending tubular reactor and atomizing reacts, in separating of stripper top realization response oil gas and spent agent, most of spent agent is subjected to inertia and gravitational motion effect to enter stripper downwards, a small amount of spent agent enters the cyclone separator group with reaction oil gas, and reaction oil gas enters down continuous fractionating column;
(2) come out from the second regenerator top temperature 700-780 ℃, carry the flue gas that contains oxygen 10-15% of catalyst micronic dust and introduce first regenerator bottoms by pipeline, be 470～600 ℃ spent agent with temperature with temperature be that the mixed catalyst that 700～780 ℃ regenerative agent forms contacts from the high-order storage tank of catalyst from stripper, heat up, burning, the catalyst time of staying 16～26s, temperature is 670～760 ℃ a regenerated flue gas, realize separating by the cyclone separator group with half regenerative agent at the first regenerator top, regenerated flue gas enters pressure energy recovery system, after reducing to 530～610 ℃, temperature enters follow-up hydrogen production process, high temperature half regenerative agent is introduced second regenerator bottoms, thereby finishes catalyst circulation;
(3) after regenerated flue gas carries out heat exchange, washing, cooling dehydration from pressure energy recovery system, send into pressure swing adsorption system separation of C O, N 2And CO 2
(4) steam and CO are sent into the middle temperature transformation system generation transformationreation that catalyst is housed, and from generate gas, separate H 2, CO 2
(5) N that separates 2The compressed nitrogen pot that enters, CO 2Collect through purifying.
The process that regenerated flue gas carries out heat exchange, washing, cooling dehydration from pressure energy recovery system is that regenerated flue gas can recovery system enter waste heat boiler from pressure, temperature enters washing system after reducing to 200～250 ℃, use ammonia-process desulfurization technique to realize that a step is finished the cooling dehydration and washing removes sulfide, nitride, temperature is reduced to below 60 ℃, enters pressure swing adsorption system by pipeline then; The all or part of pressurization cooling piece-rate system that enters of waste gas from pressure swing adsorption system comes out realizes N 2, CO 2Separation, gaseous state CO 2Make liquid or solid-state CO 2It is to become the gas that mainly contains CO from the desorption gas that pressure swing adsorption system comes out that steam and CO send into the middle temperature transformation system generation transformationreation that catalyst is housed, after heat exchanger and regenerated flue gas heat exchange, temperature rises to 180-220 ℃, mix with steam, enter transformation system together, the gas that is generated is sloughed CO through decarbonization system 2After, form hydrogen.Described first and second regenerators are the tubular type regenerator.
The method that second kind of regeneration fume from catalytic cracking prepares hydrogen and nitrogen is:
(1) burning and enter the auxiliary oven that goes into operation after main air is forced into 0.3～0.45MPa, is that 670～760 ℃ high temperature half regenerative agent contacts, burns in second regenerator bottoms with temperature from the first regenerator cyclone separator group dipleg; After introducing regenerated catalyst, introduce feedstock oil from the bottom from the lifting medium of riser from top from second regenerator, enter the top of separator, most of spent agent is subjected to inertia and gravitational motion effect to enter stripper downwards, and a small amount of spent agent enters follow-up fractionating column with reaction oil gas; CO from decarbonization system 2Enter the second regenerator middle and upper part through pipeline, introduce first regenerator bottoms from the second regenerator top with temperature 700-780 ℃, the flue gas that contains oxygen 10-15% that carries the catalyst micronic dust by pipeline, be 470～600 ℃ spent agent with temperature with temperature be that the mixed catalyst that 700～780 ℃ regenerative agent forms contacts, heats up, burns from second regenerator from stripper, the catalyst time of staying 16～26s, reacted oil gas and spent agent through the cyclone separator component from;
(2) realize separating by splitter group with half regenerative agent from the first regenerator top, temperature is that 670～760 ℃ regenerated flue gas enters pressure energy recovery system, after reducing to 530～610 ℃, temperature enters follow-up hydrogen production process, half regenerative agent is introduced second regenerator bottoms, thereby finishes catalyst circulation;
(3) after regenerated flue gas carries out heat exchange, washing, cooling dehydration from pressure energy recovery system, send into pressure swing adsorption system separation of C O, N 2And CO 2
(4) steam and CO are sent into the middle temperature transformation system generation transformationreation that catalyst is housed, and from generate gas, separate H 2, CO 2
(5) N that separates 2The compressed nitrogen pot that enters, CO 2Collect through purifying.
The process that regenerated flue gas carries out heat exchange, washing, cooling dehydration from pressure energy recovery system is that regenerated flue gas can recovery system enter waste heat boiler from pressure, temperature enters washing system after reducing to 200～250 ℃, use ammonia-process desulfurization technique to realize that a step is finished the cooling dehydration and washing removes sulfide, nitride, temperature is reduced to below 60 ℃, enters pressure swing adsorption system by pipeline then; The all or part of pressurization cooling piece-rate system that enters of waste gas from pressure swing adsorption system comes out realizes N 2, CO 2Separation, gaseous state CO 2Make liquid or solid-state CO 2It is to become the gas that mainly contains CO from the desorption gas that pressure swing adsorption system comes out that steam and CO send into the middle temperature transformation system generation transformationreation that catalyst is housed, after heat exchanger and regenerated flue gas heat exchange, temperature rises to 180-220 ℃, mix with steam, enter transformation system together, the gas that is generated is sloughed CO through decarbonization system 2After, form hydrogen.Described first is the tubular type regenerator, and second regenerator is the bed regenerator.
The method that the third regeneration fume from catalytic cracking prepares hydrogen and nitrogen is:
(1) burning and enter the auxiliary oven that goes into operation after main air is forced into 0.3～0.45MPa, is that 670～760 ℃ high temperature half regenerative agent contacts, burns in second regenerator bottoms with temperature from the first regenerator cyclone separator group dipleg; After introducing regenerated catalyst, introduce feedstock oil from the bottom from the lifting medium of riser from top from second regenerator, through thick cyclone separator and primary cyclone, most of spent agent is subjected to inertia and gravitational motion effect to enter stripper downwards, and a small amount of spent agent enters follow-up fractionating column with reaction oil gas; CO from decarbonization system 2Enter the second regenerator middle and upper part through pipeline, introduce first regenerator bottoms from the second regenerator top with temperature 700-780 ℃, the flue gas that contains oxygen 10-15% that carries the catalyst micronic dust by pipeline, be 470～600 ℃ spent agent with temperature with temperature be that the mixed catalyst that 700～780 ℃ regenerative agent forms contacts, heats up, burns from second regenerator from stripper, the catalyst time of staying 16～26s, reacted oil gas and spent agent through the cyclone separator component from;
(2) realize separating by splitter group with half regenerative agent from the first regenerator top, temperature is that 670～760 ℃ regenerated flue gas enters pressure energy recovery system, after reducing to 530～610 ℃, temperature enters follow-up hydrogen production process, half regenerative agent is introduced second regenerator bottoms, thereby finishes catalyst circulation;
(3) after regenerated flue gas carries out heat exchange, washing, cooling dehydration from pressure energy recovery system, send into pressure swing adsorption system separation of C O, N 2And CO 2
(4) steam and CO are sent into the middle temperature transformation system generation transformationreation that catalyst is housed, and from generate gas, separate H 2, CO 2
(5) N that separates 2The compressed nitrogen pot that enters, CO 2Collect through purifying.
The process that regenerated flue gas carries out heat exchange, washing, cooling dehydration from pressure energy recovery system is that regenerated flue gas can recovery system enter waste heat boiler from pressure, temperature enters washing system after reducing to 200～250 ℃, use ammonia-process desulfurization technique to realize that a step is finished the cooling dehydration and washing removes sulfide, nitride, temperature is reduced to below 60 ℃, enters pressure swing adsorption system by pipeline then; The all or part of pressurization cooling piece-rate system that enters of waste gas from pressure swing adsorption system comes out realizes N 2, CO 2Separation, gaseous state CO 2Make liquid or solid-state CO 2It is to become the gas that mainly contains CO from the desorption gas that pressure swing adsorption system comes out that steam and CO send into the middle temperature transformation system generation transformationreation that catalyst is housed, after heat exchanger and regenerated flue gas heat exchange, temperature rises to 180-220 ℃, mix with steam, enter transformation system together, the gas that is generated is sloughed CO through decarbonization system 2After, form hydrogen.Described first is the tubular type regenerator, and second regenerator is the bed regenerator.
Above-mentioned catalytic cracking unit reaction-regeneration system catalyst system therefor is a molecular sieve catalyst, generally will be called spent agent from the catalyst of the carbon distribution of stripper, the catalyst that regeneration is finished is called regenerative agent, with regenerative process carried out a part, the catalyst of not finishing whole regeneration as yet is called half regenerative agent.Regeneration is exactly that active process is burnt and recovered to the carbon distribution on the catalyst.
Compared with prior art, beneficial effect of the present invention is embodied in the following aspects:
(1) in first regenerator, belong to the combustion with meagre oxygen scope from second regenerator (or pipe) high temperature oxygen gas of coming and the regenerative response that takes place from the carbon distribution on the catalyst of stripper, temperature is about 700 ℃, with this understanding, not only the carbon distribution on the catalyst generates CO in the first regenerator middle and lower part, and the CO2 from the oxygen gas that second regenerator (or pipe) is come also can generate CO, that is: C+CO with the carbon distribution reaction on the catalyst in the first regenerator middle and upper part 2=2CO-172.3kJ/mol produces the hydrogen rate thereby increase substantially catalyst unit's carbon distribution.
(2) one main air, one flue gas, main air, flue gas flow are simple, and the main air consumption is minimum, and the pressure of flue gas can be able to fully be reclaimed.
(3) can process heavy raw oil, can control the reaction time (being generally preferred 0.5～1.5 second 0.2～3 second) flexibly, reduce coke and dry gas yied, improve 3～5 percentage points of purpose product yields.
(4) isolation technics of Du Te reaction oil gas and catalyst makes reaction oil gas needn't enter present so-called settler, reduced oil gas from catalyst separation after to time of fractionating column, heat cracking reaction reduces the productive rate that will reduce coke and dry gas.
(5) Du Te space adverse current stripping mode, the adverse current stripping when especially descending in pipeline comes out the quick stripping of the oil gas that carries on the spent agent, also can partly reduce the productive rate of coke and dry gas.
(6) air separation unit (having reduced the air separation unit investment) need not be built and N can be produced 2, also can produce liquid or solid-state CO by pressurization, cooling 2, added benefit is good.
(7) be used for existing catalytic cracking unit transformation, increase a tubular type regenerator, under the situation that does not increase the main air amount, can improve power of regeneration by a relatively large margin.
(8) regenerative system catalyst micronic dust circulation can all or part of catalytic amount that substitutes by circulating line to the first regenerator bottoms, reduces catalyst in the following time of staying of hydrothermal condition, helps the catalyst activity protection.
(9) utilization will be converted into CO originally 2CO produce H 2Equipment investments (fuel has not needed yet) such as the CO boiler of catalytic cracking unit costliness and the employed reburner of conventional device for producing hydrogen have not only been saved, and need not drop into just energy hydrogen manufacturing of raw material (as: natural gas, lighter hydrocarbons, refinery gas or coal), reduced the hydrogen manufacturing cost, the discharging of the also corresponding greenhouse gases that reduce original device for producing hydrogen, sulfide and nitride belongs to the environment protecting and power-saving project.
Description of drawings
Fig. 1,2,3 is respectively the three kinds of pairing device flow process of technical scheme simplified schematic diagram of the present invention.Among the figure: the 1st, burn main air, the 2nd, main air blower, the 3rd, auxiliary oven goes into operation, the 4th, the cyclone separator group, 5 is first regenerators, the 6th, dipleg, the 7th, high temperature, carry the oxygen gas pipeline of catalyst micronic dust, the 8th, recycling catalyst pipeline, the 9th, recycling catalyst guiding valve, 10 is second regenerators, the 11st, and reclaimable catalyst guiding valve, the 12nd, regenerated flue gas pipe, the 13rd, double slide valve, the 14th, the pipeline of falling L, the 15th, high-order storage tank, the 16th, heat removing tube, the 17th, regeneration guiding valve, the 18th, feedstock oil, the 19th, the flexible hoisting pipe, the 20th, cyclone separator, the 21st, stripper, the 22nd, reaction oil gas, the 23rd, the reclaimable catalyst pipeline, the 24th, pipe, the 25th, the regenerated catalyst pipeline, the 26th, promote medium (steam), the 27th, primary cyclone, the 28th, reprocessed oil slurry, the 29th, settler, the 30th, pressure recovery system, the 31st, waste heat boiler, the 32nd, heat exchanger, the 33rd, washing system, the 34th, pressure swing adsorption system, the 35th, flue gas leading, the 36th, air-introduced machine, the 37th, ammoniacal liquor, the 38th, compressor, the 39th, transformation system, the 40th, decarbonization system, the 41st, pipeline, the 42nd, hydrogen, the 43rd, cleaning solution, the 44th, the emptying of high point, the 45th, steam, the 46th, CO gas.
The specific embodiment
Embodiment 1: be described in detail with regard to first kind of technical scheme of the present invention below in conjunction with Fig. 1:
Burn main air 1 and enter the auxiliary oven 3 that goes into operation after by main air blower 2 pressurization, contact, burn in second regenerator, 10 bottoms with high temperature half regenerative agent, from the CO of decarbonization system 40 from first regenerator, 5 cyclone separator groups, 4 diplegs 6 2Enter the second regenerator middle and upper part through pipeline 41, enter the high-order storage tank 15 of catalyst at the second regenerator top by the pipeline of falling L 14 and realize separating of regeneration oxygen gas and regenerative agent.
Regenerative agent reacts by regeneration guiding valve 17 to the feedstock oil 18 of descending tubular reactor 19 with atomizing, in separating of stripper 21 upper pipeline realization response oil gas and carbon-contained catalyst, most of spent agent is subjected to inertia and gravitational motion effect to enter stripper 21 downwards, a small amount of spent agent enters cyclone separator group 20 with reaction oil gas, and reaction oil gas 22 enters down continuous fractionating column.
From 10 high temperature of coming, the oxygen gas that carries the catalyst micronic dust enters first regenerator, 5 bottoms by pipeline 7, with pipe 24, reclaimable catalyst pipeline 23 and reclaimable catalyst guiding valve 11 by from the catalyst (spent agent) of the carbon distribution of stripper 21 with by recycling catalyst pipeline 8, the mixed catalyst contact that 9 the regenerative agent from the high-order storage tank 15 of catalyst forms, heat up, burning, realize separating by cyclone separator group 4 with half regenerative agent at first regenerator, 5 top regenerated flue gas, regenerated flue gas about 700 ℃ enters pressure energy recovery system 30 through regenerated flue gas pipe 12, enter follow-up hydrogen production process afterwards, half regenerative agent enters second regenerator, 10 bottoms by dipleg 6, thereby finishes catalyst circulation.
Regenerated flue gas can recovery system 30 enters waste heat boiler 31 (also can recovery system 30 without pressure) by double slide valve 13 from pressure, and temperature is reduced to 200～250 ℃ and (consisted of: CO, CO 2, N 2, H 2O, NOx, SOx etc.), enter washing system 33 afterwards, use ammonia-process desulfurization technique to realize that a step is finished the cooling dehydration and washing removes sulfide, nitride, temperature is reduced to below 60 ℃, introduce ammoniacal liquor 37 by pipeline then and enter pressure swing adsorption system 34, discharge cleaning solution 43 by air-introduced machine 36.
The waste gas that comes out from pressure swing adsorption system 34 mainly consists of: N 2, CO 2, by 44 emptying of high point, another part enters compressor 38, enters nitrogen pot 43 after pressurization by a flue gas leading part.
The waste gas that comes out from pressure swing adsorption system 34 also can all or part ofly enter pressurization cooling piece-rate system, realizes N 2, CO 2Separation (not drawing among the figure), gaseous state CO 2Can make liquid or solid-state CO 2, increase new product on the one hand, reduce the discharging of greenhouse gases on the other hand.
The desorption gas that comes out from pressure swing adsorption system 34 becomes the gas 46 that mainly contains CO, behind the heat exchanger 32 and regenerated flue gas heat exchange in parallel with waste heat boiler 31, temperature rises to about 200 ℃, mixes with steam 45, enter transformation system 39 together, the gas that is generated is sloughed CO through decarbonization system 40 2After, form final purpose product---hydrogen 42.
With 800,000 tons of/year heavy oil catalytically cracking equipments of a cover processing capacity is example, and this working of an invention effect is described.
As shown in Figure 1, burn and enter the auxiliary oven that goes into operation after main air is forced into 0.3～0.45MPa (absolute pressure) by main air blower, with the temperature from the first regenerator cyclone separator group dipleg is that 670～760 ℃ of preferred 690～730 ℃ high temperature, half regenerative agents contact, burn in second regenerator bottoms, from the CO of decarbonization system 2Enter the second regenerator middle and upper part through pipeline, enter the high-order storage tank of catalyst at the second regenerator top by the pipeline of falling L and realize separating of regeneration oxygen gas and regenerative agent.
Temperature is that 660～780 ℃ of preferred regenerative agents of 670～730 ℃ are by the feedstock oil reaction of regeneration guiding valve to descending tubular reactor and atomizing, in separating of stripper upper pipeline realization response oil gas and spent agent, most of spent agent is subjected to inertia and gravitational motion effect to enter stripper downwards, a small amount of spent agent enters the cyclone separator group with reaction oil gas, and reaction oil gas enters down continuous fractionating column.
The high temperature of coming from second regenerator, the oxygen gas that carries the catalyst micronic dust enters first regenerator bottoms by pipeline, be 470～600 ℃ of preferred spent agents of 490～560 ℃ with temperature with temperature be that the mixed catalyst that 700～780 ℃ of preferred regenerative agents of 730～760 ℃ form contacts from the high-order storage tank of catalyst from stripper, heat up, burning, preferred 5～the 8m/s of gas empty bed speed 3～10m/s, the catalyst time of staying 16～26s, temperature is that 670～760 ℃ of preferred 690～730 ℃ of regenerated flue gas (form: CO/CO2=1.0～2.0) by volume, realize separating by the cyclone separator group with half regenerative agent at the first regenerator top, regenerated flue gas about 700 ℃ enters pressure energy recovery system by three supination, after reducing to 530～610 ℃, temperature enters follow-up hydrogen production process, half regenerative agent enters second regenerator bottoms by dipleg, thereby finishes catalyst circulation.
Regenerated flue gas can recovery system enter waste heat boiler from pressure, and temperature is reduced to 200～250 ℃ and (consisted of: CO, CO 2, N 2, H 2O, NOx, SOx etc.), enter washing system afterwards, use ammonia-process desulfurization technique to realize that a step is finished the cooling dehydration and washing removes sulfide, nitride, temperature is reduced to below 60 ℃, enters pressure swing adsorption system by pipeline then.
The waste gas that comes out from pressure swing adsorption system mainly consists of: N 2, CO 2, a part is by the emptying of high point, and another part enters compressor, enters nitrogen pot after pressurization.
The waste gas that comes out from pressure swing adsorption system also can all or part ofly enter pressurization cooling piece-rate system, realizes N 2, CO 2Separation (not drawing among the figure), gaseous state CO 2Can make liquid or solid-state CO 2, increase new product on the one hand, reduce the discharging of greenhouse gases on the other hand.
The desorption gas that comes out from pressure swing adsorption system becomes the gas that mainly contains CO, after heat exchanger in parallel with waste heat boiler and regenerated flue gas heat exchange, temperature rises to about 200 ℃, mixes with steam, enter transformation system together, the gas that is generated is sloughed CO through decarbonization system 2After, form final purpose product---hydrogen.
Embodiment 2: be described in detail with regard to second kind of technical scheme of the present invention below in conjunction with Fig. 2:
In Fig. 2, replaced second regenerator and the high-order storage tank of catalyst among Fig. 1 with second regenerator 10, replaced the down pipe reactor among Fig. 1 with flexible hoisting pipe 19,26 for promoting medium, 28 is reprocessed oil slurry, and 25 is the regenerated catalyst pipeline, and other is basic identical with Fig. 1.
If original catalytic cracking unit has a bed regenerator, can increase a tubular type regenerator in addition as first regenerator 5 with this bed regenerator as second regenerator 10; In order to reduce heat cracking reaction, respond and the settler part is transformed former.Burn and enter the auxiliary oven 3 that goes into operation after main air 1 is forced into 0.3～0.45MPa (absolute pressure) by main air blower 2, with the temperature from first regenerator, 5 cyclone separator groups, 4 diplegs 6 is that 670～760 ℃ of preferred 690～730 ℃ high temperature, half regenerative agents contact, burn at second regenerator 10, from the CO of decarbonization system 40 2Enter second regenerator, 10 middle and upper parts through pipeline 41, in separating of second regenerator, 10 middle and upper parts regeneration oxygen gas and regenerative agent.
Temperature is that 660～780 ℃ of preferred regenerative agents of 670～730 ℃ are by the feedstock oil reaction of regeneration guiding valve 9 to flexible hoisting pipe 19 reactors and atomizing, in separating of stripper 21 upper pipeline realization response oil gas and spent agent, most of spent agent is subjected to inertia and gravitational motion effect to enter stripper 21 downwards, a small amount of spent agent enters cyclone separator group 20 with reaction oil gas, and reaction oil gas enters down continuous fractionating column.
The high temperature of coming from second regenerator 10, the oxygen gas that carries the catalyst micronic dust enters first regenerator, 5 bottoms by pipeline, be 470～600 ℃ of preferred spent agents of 490～560 ℃ with temperature with temperature be that the mixed catalyst that 700～780 ℃ of preferred regenerative agents of 730～760 ℃ form contacts from second regenerator 10 from stripper 21, heat up, burning, preferred 5～the 8m/s of gas empty bed speed 3～10m/s, the catalyst time of staying 16～26s, temperature is that 670～760 ℃ of preferred 690～730 ℃ of regenerated flue gas (form: CO/CO2=1.0～2.0) by volume, realize separating by the cyclone separator group with half regenerative agent at the first regenerator top, regenerated flue gas about 700 ℃ enters pressure energy recovery system by three supination, after reducing to 530～610 ℃, temperature enters follow-up hydrogen production process, half regenerative agent enters second regenerator by dipleg, thereby finishes catalyst circulation.
Hydrogen manufacturing, system nitrogen part are with embodiment 1.
Embodiment 3: be described in detail with regard to the third technical scheme of the present invention below in conjunction with Fig. 3:
In Fig. 3, replaced the flexible hoisting pipe among Fig. 2 with riser reactor 19, replaced the stripper among Fig. 2 with present used settler 29,20 is thick cyclone separator, and 27 is primary cyclone, and other is basic identical with Fig. 2.
If original catalytic cracking unit has a bed regenerator, can increase a tubular type regenerator in addition as first regenerator 5 with this bed regenerator as second regenerator 10, former respond and settler 29 parts constant.Burn and enter the auxiliary oven 3 that goes into operation after main air 1 is forced into 0.3～0.45MPa (absolute pressure) by main air blower 2, with the temperature from first regenerator, 5 cyclone separator groups, 4 diplegs 6 is that 670～760 ℃ of preferred 690～730 ℃ high temperature, half regenerative agents contact, burn at second regenerator 10, from the CO of decarbonization system 40 2Enter second regenerator, 10 middle and upper parts through pipeline 41, in separating of second regenerator, 10 middle and upper parts regeneration oxygen gas and regenerative agent.
Temperature is that 660～780 ℃ of preferred regenerative agents of 670～730 ℃ are by the feedstock oil reaction of regeneration guiding valve 9 to original riser 19 reactors and atomizing, in settler 29 separating by thick cyclone separator 20 and primary cyclone 27 realization response oil gas and spent agent, spent agent enters stripping settler 29 downwards, and reaction oil gas enters down continuous fractionating column.
The high temperature of coming from second regenerator 10, the oxygen gas that carries the catalyst micronic dust enters first regenerator bottoms by pipeline 7, be 470～600 ℃ of preferred spent agents of 490～560 ℃ with temperature with temperature be that the mixed catalyst that 700～780 ℃ of preferred regenerative agents of 730～760 ℃ form contacts from second regenerator 10 from settler 29, heat up, burning, preferred 5～the 8m/s of gas empty bed speed 3～10m/s, the catalyst time of staying 16～26s, temperature is that 670～760 ℃ of preferred 690～730 ℃ of regenerated flue gas (form: CO/CO2=1.0～2.0) by volume, realize separating by cyclone separator group 4 with half regenerative agent at first regenerator, 5 tops, regenerated flue gas about 700 ℃ enters pressure energy recovery system 30 by three supination, after reducing to 530～610 ℃, temperature enters follow-up hydrogen production process, half regenerative agent enters second regenerator 10 by dipleg 6, thereby finishes catalyst circulation.
Hydrogen manufacturing, system nitrogen part are with embodiment 1.
The coking yield of general heavy oil catalytically cracking equipment is 9%, the C/H=9 of coke: 1, even press CO/CO 2Calculate at=1: 1, with the amounts of hydrogen that this flue gas generated is: 7466Nm 3/ h is equivalent to 666kg/h, or 5333 tons/year.The amounts of hydrogen that patent CN1400159A generates on the device of equal scale is: 2480 tons/year.By contrast as can be seen, the amounts of hydrogen that hydrogen production process provided by the present invention generated is more than a times of patent CN1400159A.
If this technology is used for existing catalytic cracking unit transformation, increase a tubular type regenerator, under the situation that does not increase the main air amount, not only can improve power of regeneration by a relatively large margin, can also process more multiple raw material oil, the reaction oil gas that it is unique and the isolation technics of catalyst with and unique space adverse current stripping mode, the time of shortening heat cracking reaction greatly, thereby reduce coke and dry gas yied, the purpose product yield can improve 3～5 percentage points.
This shows, utilize this technology, a spot of fund of oil refining enterprise only use not only can accomplish to improve catalytic cracking unit regenerator coke-burning capacity simultaneously, improve the purpose product yield, and its flue gas can also satisfy hydrogen manufacturing, system nitrogen needs.
Utilize this patented technology to carry out systems organization for newly-built (or enlarging) oil plant, from the angle of investment: this technology reduces the construction of air separation unit and hydrogen manufacturing conversion furnace than traditional approach, saves investment; Angle from environmental protection: this technology reduces CO 2, NOx, the discharging of SOx; From energy-conservation angle: this technology has reduced coke and dry gas yied, and the purpose product yield can improve 3～5 percentage points, has reduced hydrogen feedstock again simultaneously, has saved natural gas, lighter hydrocarbons, refinery gas or coal.

Claims (6)

1, a kind of regeneration fume from catalytic cracking prepares the method for hydrogen and nitrogen, it is characterized in that:
(1) burning and enter the auxiliary oven that goes into operation after main air is forced into 0.3～0.45MPa, is that 670～760 ℃ high temperature half regenerative agent contacts, burns in second regenerator bottoms with temperature from the first regenerator cyclone separator group dipleg, from the CO of decarbonization system 2Enter the second regenerator middle and upper part through pipeline, enter the high-order storage tank of catalyst by the second regenerator top and realize separating of regeneration oxygen gas and regenerative agent; Temperature is that 660～780 ℃ regenerative agent to the feedstock oil of descending tubular reactor and atomizing reacts, in separating of stripper top realization response oil gas and spent agent, most of spent agent is subjected to inertia and gravitational motion effect to enter stripper downwards, a small amount of spent agent enters the cyclone separator group with reaction oil gas, and reaction oil gas enters down continuous fractionating column;
(2) come out from the second regenerator top temperature 700-780 ℃, carry the regeneration oxygen gas that contains oxygen 10-15% of regenerative agent micronic dust and introduce first regenerator bottoms by pipeline, be 470～600 ℃ spent agent with temperature with temperature be that the mixed catalyst that 700～780 ℃ regenerative agent forms contacts from the high-order storage tank of regenerative agent from stripper, heat up, burning, the mixed catalyst time of staying 16～26s, temperature is 670～760 ℃ a regenerated flue gas, realize separating by the cyclone separator group with half regenerative agent at the first regenerator top, regenerated flue gas enters pressure energy recovery system, after reducing to 530～610 ℃, temperature enters follow-up hydrogen production process, high temperature half regenerative agent is introduced second regenerator bottoms, thereby finishes catalyst circulation;
(3) regenerated flue gas can recovery system come out to enter the waste heat boiler heat exchange from pressure, temperature enters washing system after reducing to 200～250 ℃, use ammonia-process desulfurization technique to realize that a step is finished the cooling dehydration and washing removes sulfide, nitride, temperature is reduced to below 60 ℃, enter pressure swing adsorption system by pipeline then, the all or part of pressurization cooling piece-rate system that enters of waste gas from pressure swing adsorption system comes out realizes N 2, CO 2Separation, gaseous state CO 2Make liquid or solid-state CO 2
(4) steam and CO are sent into the desorption gas that comes out from pressure swing adsorption system after the middle temperature transformation system generation transformationreation that catalyst is housed and become the gas that mainly contains CO, after heat exchanger and regenerated flue gas heat exchange, temperature rises to 180-220 ℃, mix with steam, enter transformation system together, the gas that is generated is sloughed CO through decarbonization system 2After, form hydrogen;
(5) N that separates 2The compressed nitrogen pot that enters, CO 2Collect through purifying.
2, regeneration fume from catalytic cracking according to claim 1 prepares the method for hydrogen and nitrogen, it is characterized in that: described first and second regenerators are the tubular type regenerator.
3, a kind of regeneration fume from catalytic cracking prepares the method for hydrogen and nitrogen, it is characterized in that:
(1) burning and enter the auxiliary oven that goes into operation after main air is forced into 0.3～0.45MPa, is that 670～760 ℃ high temperature half regenerative agent contacts, burns in second regenerator bottoms with temperature from the first regenerator cyclone separator group dipleg; After the lifting medium of riser is introduced feedstock oil from the bottom introducing from the regenerative agent of second regenerator, from top, enter the top of separator, most of spent agent is subjected to inertia and gravitational motion effect to enter stripper downwards, and a small amount of spent agent enters follow-up fractionating column with reaction oil gas; CO from decarbonization system 2Enter the second regenerator middle and upper part through pipeline, introduce first regenerator bottoms from the second regenerator top with temperature 700-780 ℃, the flue gas that contains oxygen 10-15% that carries the regenerative agent micronic dust by pipeline, be 470～600 ℃ spent agent with temperature with temperature be that the mixed catalyst that 700～780 ℃ regenerative agent forms contacts, heats up, burns from second regenerator from stripper, the mixed catalyst time of staying 16～26s, reacted oil gas and spent agent through the cyclone separator component from;
(2) regenerated flue gas is realized separating by the cyclone separator group with half regenerative agent from the first regenerator top, temperature is that 670～760 ℃ regenerated flue gas enters pressure energy recovery system, after reducing to 530～610 ℃, temperature enters follow-up hydrogen production process, half regenerative agent is introduced second regenerator bottoms, thereby finishes catalyst circulation;
(3) regenerated flue gas can recovery system enter the waste heat boiler heat exchange from pressure, temperature enters washing system after reducing to 200～250 ℃, use ammonia-process desulfurization technique to realize that a step is finished the cooling dehydration and washing removes sulfide, nitride, temperature is reduced to below 60 ℃, enter pressure swing adsorption system by pipeline then, the all or part of pressurization cooling piece-rate system that enters of waste gas from pressure swing adsorption system comes out realizes N 2, CO 2Separation, gaseous state CO 2Make liquid or solid-state CO 2
Regenerated flue gas is sent into pressure swing adsorption system separation of C O, N after carrying out heat exchange, washing, cooling dehydration from pressure energy recovery system 2And CO 2
(4) steam and CO are sent into the desorption gas that comes out from pressure swing adsorption system after the middle temperature transformation system generation transformationreation that catalyst is housed and become the gas that mainly contains CO, after heat exchanger and regenerated flue gas heat exchange, temperature rises to 180-220 ℃, mix with steam, enter transformation system together, the gas that is generated is sloughed CO through decarbonization system 2After, form hydrogen;
(5) N that separates 2The compressed nitrogen pot that enters, CO 2Collect through purifying.
4, regeneration fume from catalytic cracking according to claim 3 prepares the method for hydrogen and nitrogen, it is characterized in that: described first regenerator is the tubular type regenerator, and second regenerator is the bed regenerator.
5, a kind of regeneration fume from catalytic cracking prepares the method for hydrogen and nitrogen, it is characterized in that:
(1) burning and enter the auxiliary oven that goes into operation after main air is forced into 0.3～0.45MPa, is that 670～760 ℃ high temperature half regenerative agent contacts, burns in second regenerator bottoms with temperature from the first regenerator cyclone separator group dipleg; After introducing regenerative agent, introduce feedstock oil from the bottom from the lifting medium of riser from top from second regenerator, through thick cyclone separator and primary cyclone, most of spent agent is subjected to inertia and gravity effect to enter stripper downwards, and a small amount of spent agent enters follow-up fractionating column with reaction oil gas; CO from decarbonization system 2Enter the second regenerator middle and upper part through pipeline, introduce first regenerator bottoms from the second regenerator top with temperature 700-780 ℃, the flue gas that contains oxygen 10-15% that carries the regenerative agent micronic dust by pipeline, be 470～600 ℃ spent agent with temperature with temperature be that the mixed catalyst that 700～780 ℃ regenerative agent forms contacts, heats up, burns from second regenerator from stripper, the mixed catalyst time of staying 16～26s, reacted oil gas and spent agent through the cyclone separator component from;
(2) regenerated flue gas is realized separating by the cyclone separator group with half regenerative agent from the first regenerator top, temperature is that 670～760 ℃ regenerated flue gas enters pressure energy recovery system, after reducing to 530～610 ℃, temperature enters follow-up hydrogen production process, half regenerative agent is introduced second regenerator bottoms, thereby finishes catalyst circulation;
(3) regenerated flue gas is from the pressure waste heat boiler heat exchange of can recovery system coming out, temperature enters washing system after reducing to 200～250 ℃, use ammonia-process desulfurization technique to realize that a step is finished the cooling dehydration and washing removes sulfide, nitride, temperature is reduced to below 60 ℃, enter pressure swing adsorption system by pipeline then, the all or part of pressurization cooling piece-rate system that enters of waste gas from pressure swing adsorption system comes out realizes N 2, CO 2Separation, gaseous state CO 2Make liquid or solid-state CO 2
(4) steam and CO are sent into the desorption gas that comes out from pressure swing adsorption system after the middle temperature transformation system generation transformationreation that catalyst is housed and become the gas that mainly contains CO, after heat exchanger and regenerated flue gas heat exchange, temperature rises to 180-220 ℃, being mixed with steam enters transformation system, and the gas that is generated is sloughed CO through decarbonization system 2After, form hydrogen steam and CO and send into the middle temperature transformation system generation transformationreation that catalyst is housed, and from generate gas, separate H 2, CO 2
(5) N that separates 2The compressed nitrogen pot that enters, CO 2Collect through purifying.
6, regeneration fume from catalytic cracking according to claim 5 prepares the method for hydrogen and nitrogen, it is characterized in that: described first regenerator is the tubular type regenerator, and second regenerator is the bed regenerator.
CN200710017069A 2007-09-07 2007-09-07 Method for preparing hydrogen and nitrogen by catalytic cracking regenerative fume Expired - Fee Related CN100594966C (en)

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