CN101920187B - Equipment and method for preparing low-carbon olefins by cracking reactions - Google Patents
Equipment and method for preparing low-carbon olefins by cracking reactions Download PDFInfo
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- CN101920187B CN101920187B CN 201010284541 CN201010284541A CN101920187B CN 101920187 B CN101920187 B CN 101920187B CN 201010284541 CN201010284541 CN 201010284541 CN 201010284541 A CN201010284541 A CN 201010284541A CN 101920187 B CN101920187 B CN 101920187B
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- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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- B01J12/00—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor
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- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/26—Nozzle-type reactors, i.e. the distribution of the initial reactants within the reactor is effected by their introduction or injection through nozzles
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- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
- B01J4/002—Nozzle-type elements
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- B01J2219/00051—Controlling the temperature
- B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
- B01J2219/00076—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements inside the reactor
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- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
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- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
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Abstract
The invention provides a reactor for preparing low-carbon olefins by cracking reactions, which has an entrance end (1) and an exit end (2), wherein the two ends are formed at opposite positions on the reactor; one fourth of the space from the entrance end (1) in the reactor is a combustion zone (3) and the rest space is a reaction area (4); the entrance end (1) is provided with a fuel and oxygen nozzle (5) communicated with the combustion zone (3), and the end ports except the nozzle are sealed; a reactor side wall between the combustion zone (3) and the reaction area (4) is provided with a raw material nozzle (6) and the exit end (2) has a product outlet (7); and the fuel and oxygen nozzle (5) and the raw material nozzle (6) are one or more than two nozzle structures. The invention also provides a method for preparing the low-carbon olefins by using the reactor.
Description
Technical field
The present invention relates to a kind of petrochemical process, further relate to a kind of equipment and method of preparing low-carbon olefins by cracking reactions.
Background technology
The production technology of ethene and propylene all adopts the tubular process steam cracking technology both at home and abroad at present; Be that cracking stock is carrying out heat scission reaction with steam as diluent in the tubular type boiler tube under the condition of high temperature, short residence time and low hydrocarbon partial pressure; Produce ethene, propylene, and products such as by-product C 4 olefin, carbon five, drippolene.History of this technology existing decades, representational patented technology have the Lin De (LIND) etc. of Lu Musi (LUMMUS), Si Wei (S.W), Kellogg (KBR) and the Germany of the U.S..Typical olefin production processes flow process mainly contains cracking, chilling, compression, several big operations of separation; Having patented technology representational is the cracking unit; Cracking technique is the key of olefin production technology, and it directly influences the production of each item technical-economic index and safety and stability.
The production procedure of tubular process steam cracking technology is: the cracking stock after the preheating gets into the convection section heat temperature raising of tube cracking furnace; Dilution steam generation also in the certain position of convection section according to a certain percentage (generally being 0.5-0.8) inject cracking stock heating and gasifying simultaneously, make temperature go out the heat decomposition temperature that reaches raw material when convection section gets into radiant section; At radiant section, raw material is rapidly heated in extremely short time 0.1-0.5 second and carries out heat scission reaction, generates ethylene, propylene and other product, fast the cracking logistics is quenched to 500 ℃ of following cessation reactions and reclaims its heat of high temperature by quenching boiler in the radiant section outlet; Cracking gas behind the chilling gets into next quench oil, chilled water (chw) unit and compression separative element, further separates and reclaims ethene, propylene, C4 hydrocarbon and other product.
The core of tube furnace steam cracking technology is the technology and the equipment of pyrolysis furnace.In decades should technology update at aspects such as the material of the type of furnace, boiler tube size and arrangement mode and boiler tube, burners and improve, remain the major technique of current domestic and international olefin production, have consequence and effect at petrochemical industry.However, the tubular type steam cracking technology also exists certain deficiency and difficult bad solution, mainly contains following aspect:
(1) hydrocarbon cracking requires the reaction condition of high temperature, short residence time, requires boiler tube will have very high heat flux and good high-temperature mechanical performance.Even if but use best material at present, and the boiler tube tube wall temperature upper limit also can only allow to reach 1150 ℃, and the restriction of this wall temperature makes that further to improve the cracking severity difficulty more very big.
(2) hydro carbons such as cracking stock such as naphtha, tail oil is in cracking reaction; Except that generating ethylene, propylene, also can generate tar and coke; They are deposited on boiler tube inwall green coke and stop up boiler tube; Can cause the flow of a certain road boiler tube to descend, and, must stop charging and burn or the blowing out mechanical decoking because flow reduces and tube wall temperature raise surpass permissible value.The coke cleaning period of general pyrolysis furnace is 40-60 days, and operation is burnt in each completion will use 2-3 days.So periodic coke cleaning operation has not only reduced the utilization of capacity of pyrolysis furnace, and the quantity of stove also will be increased accordingly.Regular in addition stove handover operation can influence the security and stability of production.
(3) ability of present large-scale pyrolysis furnace separate unit is ten thousand tons of ethene of 10-15/year platforms; Scale is that 1,000,000 tons/year ethylene unit will dispose 7-10 platform pyrolysis furnace; Because the expensive cost of the fee of material of boiler tube is high; The investment in stove district will account for the about 1/3 of full device, and this has apparent influence to the investment of olefin production and cost.
(4) at present the cracking stock used of ethene factory is naphtha more than 60%, also has ethane, propane, carbon fourth class light hydrocarbon component, and heavier only accounts for 10-30% like light diesel fuel, hydrogenation tail oil.These chemical industry light oil and lighter hydrocarbons that are used as cracking stock are all from oil plant, and along with the continuous increase of alkene demand is becoming tight chemical industry light oil supply day, the contradiction of resource distribution can be outstanding all the more.Therefore enlarge raw material sources, improve cracker the adaptability of raw material range is become the task of top priority.
(5) pyrolysis in tubular furnace system alkene need consume a large amount of fuel, and the thermal efficiency of tubular heater is generally 92-94%, and the thermal loss that has 6-8% has a large amount of CO simultaneously in atmosphere
2, CO, NO, NO
2Row is to atmosphere, and environmental pollution is bigger.
In view of the defective of above-mentioned prior art, the present invention proposes a kind of new low carbon olefin preparation method and equipment, has overcome the deficiency of prior art, can improve the level of production of alkene industry.
Summary of the invention
The objective of the invention is to: a kind of reactor that is used for preparing low-carbon olefins by cracking reactions is provided, and the process of utilizing this reactor made low-carbon alkene.
Above-mentioned purpose of the present invention realizes through following technical scheme:
A kind of reactor that is used for preparing low-carbon olefins by cracking reactions is provided, have the arrival end 1 and the port of export 2, and these two ends is in relative position on reactor; Inside reactor is combustion zone 3 from 1/4 space of arrival end, and its complementary space is a reaction zone 4; Said arrival end 1 is provided with fuel and the oxygen jet 5 that leads to combustion zone 3, and the port beyond this nozzle seals; On the sidewall of reactor between said combustion zone 3 and the reaction zone 4, be provided with raw material nozzles 6, the said port of export 2 is provided with product outlet 7; Described fuel and oxygen jet 5 are one or more nozzle arrangements with raw material nozzles 6.
The arrival end 1 of said reactor and the internal diameter of the port of export 2 are preferably less than the internal diameter of reaction zone 4.
Said arrival end 1 inside preferably is variable-diameter structure, further preferably is Venturi tube structure.
Said reaction zone 4 inside are provided with flow restriction 8, take place with the air-teturning mixed phenomenon that reduces internal gas flow as far as possible; Said flow restriction is the current limiting plate of preferred some axial distribution further.
3 middle parts, described combustion zone preferably are provided with temperature adjustment steam inlet 9.
Described combustion zone 3 can also be provided with cooling device 10 at outer wall, preferred cooling jacket, interlayer or coil pipe.
In addition, reactor of the present invention can also be provided with various control equipment, and for example: said raw material nozzles place is provided with feed distributor; Be provided with sonde-type flame combustion detection system in the combustion zone; Low spot at reaction zone is provided with dust exhaustor and dust discharge outlet; Middle part, described combustion zone is provided with flow distributor etc.
Said reactor linings material can use the fire-resistant heat insulating material of various routines.
Described reactor inlet end can be connected with existing fuel, oxygen supply system according to conventional method; Said raw material nozzles can be connected with existing cracking stock pre-heating system according to conventional method; The said port of export can be connected with existing fast cooling device according to conventional method.
Reactor of the present invention can be prepared into any petrochemical industry industry acceptable response device shape; Also can use with the acceptable form of the industry of petrochemical industry arbitrarily such as vertical, horizontal; And do not limit the upper and lower or left and right position of the said arrival end and the port of export.
The present invention also provides a kind of process of utilizing above-mentioned reactor through preparing low-carbon olefins by cracking reactions, may further comprise the steps:
1) preheating cracking stock to 150～700 ℃;
2) let fuel and oxygen burn the CO of generation through the fuel of said reactor and the combustion zone of oxygen jet 5 entering reactors according to the ratio of completing combustion
2, H
2O and flue-gas temperature remain on 1000～1500 ℃;
3) step 1) is handled the flow of feed gas that obtains and is got into described reactor through the raw material nozzles 6 of said reactor; With step 2) the quick contact heat-exchanging of high-temperature gas that produces of burning; Raw material is warming up to 800～1000 ℃ rapidly and carries out cracking reaction; The cracking reaction time (time of staying) is 0.1-0.3 second, and reaction pressure contains low-carbon alkene, methane, hydrogen and other byproducts at 0.1-0.5MPa in the cracking gas that reaction generates;
In the above-mentioned cracking reaction, the temperature of reaction and time of staying difference to some extent by the different of raw material, the cracking temperature of naphtha is 820-900 ℃, and light diesel fuel is 800-860 ℃, and lighter hydrocarbons are 850-900 ℃, and heavy oil is 750～850.As a whole, the temperature of the cracking reaction of present technique is than the high 5-50 of existing tube oven method ℃; The time of staying is confirmed when reactor designs, because raw material of the present invention is directly to heat through fuel combustion, therefore heat conduction can reduce to 0.1-0.3 second with the time of staying very rapidly, reduced by 0.2 second than pyrolysis in tubular furnace method; Reaction pressure also has apparent reduction; Because the structure of reactor difference significantly reduces the reaction system pressure drop; Burning generates in the method for the present invention in addition carbon dioxide and steam are the hydrocarbon partial pressures that is used to reduce raw material hydrocarbon as diluent again; Therefore the pressure of cracking reaction is lower than existing tubular process, and between 0.1-0.5MPa, practical operation pressure is regulated and control by follow-up chilling system.
In addition, in the above-mentioned reaction, get in the unit interval reactor material quantity can according to the annual production of reactor with calculate a year on-stream time after confirm.
4) the product cracking gas of the reaction of step 3) generation is cooled to below 500 ℃ through the product outlet 7 direct cooling devices that get into of said reactor; Stopping secondary response and to reclaim heat of high temperature, and then finally obtain the low-carbon alkene of polymer grade quality through over-quenching, compression, deep cooling and separating step; Also need carry out purified treatment in the described compression process, promptly take off CO
2, sour gas and water.Shown in the visible accompanying drawing 3 of flow.
The preferred lighter hydrocarbons of the described cracking stock of step 1) (as, liquefied petroleum gas (LPG), liquefied natural gas (LNG), ethane, propane, butane etc.), naphtha, light diesel fuel cut, heavy diesel fuel cut, hydrogenation tail oil or heavy oil etc.
The described preheating of step 1) can be through heat exchanger or heating furnace heating.
Step 1) can also adopt existing method to carry out suitably gasification process according to raw material properties except preheating, for example in raw material, feeds water vapour.
Step 2) described fuel preferred gas fuel or liquid fuel.
The mixture or the natural gas of the preferred ethane of described gaseous fuel, propane, ethane and propane; The preferred gasoline of described liquid fuel, diesel oil or ethanol.
Step 2) described fuel and the oxygen flow that gets into reactor is confirmed according to the DESIGN OF REACTOR ability; And it is relevant with the kind of cracking stock; The heat that common cracking stock cracking reaction per ton needs fuel to provide is about 2.5-4.0GJ; Can converse the needed firing rate of different material in view of the above, and the designed capacity of association reaction device confirms that finally fuel and oxygen get into the flow of reactor.
Step 2) high-temperature flue-gas that generates of said fuel and oxygen combustion can be regulated through the control fuel flow rate, preferably controls the mode that fuel flow rate combines to feed temperature adjustment steam and carries out dual regulation.
The described cracking reaction temperature controlling of step 3) can realize through multiple existing method; Also can realize through the feeding amount and/or the temperature adjustment steam flow of fuel metering; Concrete grammar can be: upper, middle and lower and cracked gas at combustion zone and reactor are established a plurality of temperature survey points in the pipeline of cooling device; Be provided with the measurement and the ratio conditioning equipment of fuel flow rate and oxygen flow simultaneously; The cracking severity that the operator can reach according to the character and the needs of cracking stock is set reaction temperature, and temperature control system can automatic regulate fuel flow, oxygen flow and/or temperature adjustment steam flow accordingly.
Can also isolated methane of the described separating step of step 4) and hydrogen as fuel be got back to step 2 once more) reactor cycles use; Isolated other byproducts of the described separating step of step 4) are got back to step 1) once more as raw material carry out preheating.
Above-mentioned temperature adjustment steam both can get into reactor through the temperature adjustment steam inlet 9 of reactor, also can get into reactor through raw material nozzles 6 together with raw material.
Compare with existing tubular process steam cracking technology, the present invention makes the condition of cracking system alkene that bigger change arranged through the change to reactor and technological process and technological parameter, and the beneficial effect that produces at technical elements is mainly reflected in:
1. the reaction of the thermal cracking process to prepare lower olefine of hydro carbons is not carried out in the tube furnace boiler tube; But in raw material hydrocarbon and reactor that fuel directly contacts, carry out; Can overcome or showing the weak point of improving the tube furnace steam splitting process; The air-flow that makes burning constantly, directly, to cracking stock heat is provided apace can be easy to realize the condition of high temperature short reaction time.
2. the reactor of pyrolysis in tubular furnace technology needs up to a hundred groups boiler tube, and the boiler tube that pyrolysis furnace is the 50-80 millimeter by tens groups of diameters is formed, and the pressure drop of boiler tube is bigger, and 0.2-0.3MPa is arranged.And structure of reactor of the present invention is simple and direct, and volume is big, and the pressure drop of raw material and product is estimated to reduce 0.1-0.15MPa, on the other hand, in the present invention, with the CO of burning generation
2And H
2O uses as the diluent gas that reduces hydrocarbon partial pressure, does not add that thinner ratio can reach 30-50% under the situation of steam.More than two combined factors get up, the hydrocarbon partial pressure of present technique cracking reaction raw material is under the situation that dilution steam generation uses no or little, than the low 30-40% of tubular process technology.
3. because structure of reactor characteristics of the present invention are difficult for coking, easy and simple to handle, can process raw material, like hydrogenation tail oil, heavy diesel fuel, heavy oil etc. than heavy end.
Benefit aspect economic benefit and environmental protection is set forth as follows:
1),, see the following form shown in 1 because the further improvement of crack reacting condition makes the productive rate of ethene and propylene can increase 1-5% approximately as far as same cracking stock:
Table 1.
2) make the investment of cracking unit and supporting part can reduce 20-30%, the construction period shortens, and the high-temperature alloy steel consumption significantly reduces.
3) present technique is applicable to the cracking stock than heavy; The component and the scope of low-carbon alkene raw material have been widened; More existing tube furnace steam cracking technology has reduced the increment of ethylene, propylene in the petrochemical industry development to oil product, especially the degree of dependence of chemical industry light oil demand.
4) energy consumption of ethylene, propylene and production cost reduce 5-10%, move safety and stability more.
5) because the CO in firing rate minimizing and the cracking reaction gas
2Can recycle, make the fume emission rich and influential family of ethene factory---the smoke discharge amount of cracking unit reduces 30-40%.Have bigger contribution to improving environmental condition.
Description of drawings
Accompanying drawing 1 is the structure cutaway view of embodiment 1 described reactor.
Accompanying drawing 2 is the structure cutaway view of embodiment 2 described reactors.
Accompanying drawing 3 prepares the general flow chart of low-carbon alkene method for the present invention.
The specific embodiment
A kind ofly be used for the reactor that heat scission reaction prepares low-carbon alkene, duty is vertical, and its structure is seen accompanying drawing 1, comprises the arrival end 1 that is in top and the port of export 2 that is in the bottom.Wherein, in arrival end 1 inside, the space that accounts for whole reactor length 1/4 is combustion zone 3, its complementary space is a reaction zone 4, and whole combustion zone 3 space inwalls are the venturi type variable-diameter structure.The arrival end center inwardly is provided with 1 fuel and oxygen jet 5, and 3 middle parts are provided with temperature adjustment steam jet 9 in the combustion zone, and hole enlargement place of 3 entering reaction zones 4 is provided with 3 raw material nozzles 6 in the combustion zone; The port of export 2 is provided with product outlet 7.In addition, 6 places also are provided with flow control system and feed distributor in raw material nozzles, also are provided with flow control system at fuel and oxygen jet 5 places, and 3 inside are provided with sonde-type flame combustion detection system in the combustion zone.
A kind ofly be used for the reactor that heat scission reaction prepares low-carbon alkene, duty is horizontal, and its structure is seen accompanying drawing 2, comprises the arrival end 1 that is in the left side and the port of export 2 that is in the right side.Wherein, in arrival end 1 inside, the space that accounts for whole reactor length 1/4 is combustion zone 3, its complementary space is a reaction zone 4, and whole combustion zone 3 space inwalls become the venturi type variable-diameter structure, and the combustion zone outer wall is provided with cooling jacket 10.The arrival end center inwardly is provided with 3 fuel and oxygen jet 5, and 3 middle parts are provided with temperature adjustment steam jet 9 in the combustion zone, and hole enlargement place of 3 entering reaction zones 4 is provided with 3 raw material nozzles 6 in the combustion zone; The port of export 2 is provided with product outlet 7.In addition, 6 places also are provided with flow control system and feed distributor in raw material nozzles, also are provided with flow control system at fuel and oxygen jet 5 places, and 3 inside are provided with sonde-type flame combustion detection system in the combustion zone.
A kind of reactor that is used for preparing low-carbon olefins by cracking reactions, duty are vertical, and its structure is seen accompanying drawing 1, comprise the arrival end 1 that is in the bottom and the port of export 2 that is in top.Wherein in arrival end 1 inside, the space that accounts for whole reactor length 1/4 is combustion zone 3, its complementary space is a reaction zone 4, the internal diameter of combustion zone 3 inwardly is provided with 2 fuel and oxygen jet 5 less than the internal diameter of reaction zone 4 in arrival end 1 center; Hole enlargement place that combustion zone 3 gets into reaction zone 4 is provided with 1 inside raw material nozzles 6; The port of export 2 is provided with product outlet 7; Also be provided with the current limiting plate 8 that 5 axially parallels distribute in the inner space of reaction zone 4.In addition, 6 places also are provided with flow control system and feed distributor in raw material nozzles, also are provided with flow control system at fuel and oxygen jet 5 places, and 3 inside are provided with sonde-type flame combustion detection system in the combustion zone.
A kind of is the method for raw material through preparing low-carbon olefins by cracking reactions with the naphtha, selects the reactor of embodiment 2 to carry out, and may further comprise the steps:
1) passes through heat exchanger preheating naphtha to 580-650 ℃,, in warm, inject quantities simultaneously, make its rate of gasification reach 100% with near its cracking temperature;
2) be fuel with natural gas or methane, spray in the reactor through the fuel of reactor and oxygen jet 5 according to the ratio of completing combustion with oxygen and burn, generate CO
2And H
2O sprays into temperature adjustment steam through temperature adjustment steam jet 9 in reactor, make combustion zone 3 temperature remain on 1100～1300 ℃ of intervals;
3) handle the flow through raw material nozzles 6 of reactor of the naphtha gas obtain through step 1) and spray into the reaction zone 4 of reactor; With step 2) in 3 burnings produce in the combustion zone the quick contact heat-exchanging of high-temperature gas; The naphtha air-flow heats up rapidly, and fuel metering and material flow make reaction temperature be controlled at 820-900 ℃ of interval, carry out cracking reaction; About 0.2 second of the time of cracking reaction, reaction pressure is controlled at 0.1-0.3MPa.The cracking gas that reaction generates contains the ethene 32.5% (w/w) of having an appointment, and propylene 16.8% (w/w) also contains hydrogen, methane, butadiene, gasoline aromatic hydrocarbons, fuel oil and other byproduct in addition;
4) cracking gas that generates of the reaction of step 3) directly gets into quenching boilers through the product outlet 7 of said reactor and is cooled to below 500 ℃, stopping secondary response and to reclaim heat of high temperature, and then (sloughs water, CO simultaneously through quenching unit, compression unit
2And sour gas), cryogenic unit and separative element are handled final low-carbon alkene ethene and the propylene that obtains the polymer grade quality; The heat that quenching boiler reclaims is used to take place high steam and supplies full factory to use.
A kind of is the method for raw material through preparing low-carbon olefins by cracking reactions with the hydrogenation tail oil, selects the reactor of embodiment 3 to carry out, and may further comprise the steps:
1) passes through heating furnace preheating hydrogenation tail oil to 500-580 ℃,, in heating process, inject water vapour simultaneously, make its rate of gasification reach 90% with near its cracking temperature;
2) with the natural gas be fuel, burn in the combustion zone 3 that the fuel and the oxygen jet 5 of reactor sprays into reactor according to the ratio of completing combustion, generate CO with oxygen
2And H
2O makes the temperature of combustion zone 3 remain on 1200～1300 ℃;
3) handle the hydrogenation tail oil air-flow that obtains sprays into reactor through the raw material nozzles 6 of reactor reaction zone 4 through step 1); With step 2) in 3 burnings produce in the combustion zone the quick contact heat-exchanging of high-temperature gas, the hydrogenation tail oil air-flow is warming up to 830-850 ℃ rapidly and carries out cracking reaction, the time of cracking reaction is 0.2 second; Reaction pressure is 0.2-0.4MPa; In the entire reaction course, the back-mixing of the current limiting plate 8 control air-flows that are provided with through inside reactor, the cracking gas that reaction generates contains ethene 31.5% (w/w) approximately; Propylene 16.2% (w/w) also contains hydrogen, methane, butadiene, gasoline aromatic hydrocarbons, fuel oil and other accessory substance in addition;
4) cracking gas that generates of the reaction of step 3) directly gets into quenching boilers through the product outlet 7 of said reactor and is cooled to below 500 ℃, stopping secondary response and to reclaim heat of high temperature, and then (sloughs water, CO simultaneously through quenching unit, compression unit
2And sour gas), cryogenic unit and separative element are handled final low-carbon alkene, methane, hydrogen and other accessory substances that obtains the polymer grade quality in back;
5) step 4) separated hydrogen and methane are returned step 2 through pipeline), acting as a fuel gets into reactor through fuel and oxygen jet 5, substitutes the initial natural gas that uses gradually; Other accessory substances are returned step 1) as raw material; The heat that quenching boiler reclaims is used to take place high steam and supplies full factory to use.
A kind of is the method for raw material through preparing low-carbon olefins by cracking reactions with the liquefied petroleum gas, selects the reactor of embodiment 2 to carry out, and may further comprise the steps:
1) through heating furnace preheating liquefied petroleum gas to 550-650 ℃, with near its cracking temperature, and make its gasification ratio reach 100%;
2) mist with methane and ethane is a fuel, in the combustion zone 3 that the fuel and the oxygen jet 5 of reactor sprays into reactor, burns according to the ratio of completing combustion with oxygen, generates CO
2And H
2O sprays into temperature adjustment steam through temperature adjustment steam jet 9 in reactor, make combustion zone 3 temperature remain on 1300～1500 ℃; Cooling jacket 10 through combustion zone 3 outer walls reclaims heat simultaneously;
3) handle the liquefied petroleum entraining air stream that obtains sprays into reactor through the raw material nozzles 6 of reactor reaction zone 4 through step 1); With step 2) in 3 burnings produce in the combustion zone the quick contact heat-exchanging of high-temperature gas; The liquefied petroleum entraining air stream is warming up to 860-920 ℃ rapidly and carries out cracking reaction; The time of cracking reaction is 0.1-0.2 second, and reaction pressure is controlled at 0.2-0.5MPa, and the cracking gas that reaction generates contains has ethene 30.8% (w/w) approximately; Propylene 15.7% (w/w) also contains hydrogen, methane, butadiene, gasoline aromatic hydrocarbons, fuel oil and other accessory substance in addition;
4) cracking gas that generates of the reaction of step 3) directly gets into quenching boilers through the product outlet 7 of said reactor and is cooled to below 500 ℃, stopping secondary response and to reclaim heat of high temperature, and then (sloughs water, CO simultaneously through quenching unit, compression unit
2And sour gas), cryogenic unit and separative element are handled final low-carbon alkene, methane, hydrogen and other accessory substances that obtains the polymer grade quality in back;
5) step 4) separated hydrogen and methane are returned step 2 through pipeline), acting as a fuel gets into reactor through fuel and oxygen jet 5, substitutes initial methane, the ethane gaseous mixture that uses gradually; Isolated other accessory substances are returned step 1) as raw material; The heat that quenching boiler reclaims is used to take place high steam and supplies full factory to use.
A kind of is the method for raw material through preparing low-carbon olefins by cracking reactions with residual oil, selects the reactor of embodiment 2 to carry out, and may further comprise the steps:
1) through heating furnace preheating residual oil to 250-350 ℃, with near its cracking temperature and regulate the requirement that its viscosity meets atomizer;
2) with diesel oil be fuel, burn in the combustion zone 3 that the fuel and the oxygen jet 5 of reactor sprays into reactor according to the ratio of completing combustion, generate CO with oxygen
2And H
2O sprays into temperature adjustment steam through temperature adjustment steam jet 9 in reactor, make combustion zone 3 temperature remain on 1000～1200 ℃; Cooling jacket 10 through combustion zone 3 outer walls reclaims heat simultaneously;
3) handle the residual oil that obtains sprays into reactor through the raw material nozzles 6 of reactor reaction zone 4 through step 1); With step 2) in 3 burnings produce in the combustion zone the quick contact heat-exchanging of high-temperature gas; Residual oil is warming up to 760-820 ℃ rapidly and carries out cracking reaction; The time of cracking reaction is 0.1-0.2 second, and reaction pressure is controlled at 0.2-0.5MPa, and the cracking gas that reaction generates contains has ethene 27.2% (w/w) approximately; Propylene 13.5% (w/w) also contains hydrogen, methane, butadiene, gasoline aromatic hydrocarbons, fuel oil and other accessory substance in addition;
4) cracking gas of the reaction of step 3) generation directly gets into quencher through the product outlet 7 of said reactor; By the quench oil that sprays into its temperature is cooled to below 450 ℃; Stopping secondary response and to reclaim heat of high temperature, and then (slough water, CO simultaneously through quenching unit, compression unit
2And sour gas), cryogenic unit and separative element are handled final low-carbon alkene, methane, hydrogen and other accessory substances that obtains the polymer grade quality in back;
5) step 4) separated hydrogen and methane are returned step 2 through pipeline), acting as a fuel gets into reactor through fuel and oxygen jet 5, substitutes initial methane, the ethane gaseous mixture that uses gradually; Isolated other accessory substances are returned step 1) as raw material; The heat that quenching boiler reclaims is used to take place high steam and supplies full factory to use.
Ethylene production capacity is 300,000 tons/year a ethylene unit, and cracking stock is a naphtha, product be annual 300000 tons of purity be 99.9% ethene, 150,000 ton 99.5% propylene, also have butadiene, C5, drippolene, tar etc.; The utilization of capacity is 8000 hours/year;
1) the feed naphtha flow be 124 tons/time, temperature reaches 150 ℃ of entering preheating furnaces after heat exchange, add at preheating furnace middle part 12 tons/time gasification steam, outlet temperature is 550-600 ℃;
2) fuel natural gas and oxygen are by the fuel and the oxygen jet 5 entering combustion zones 3 of reactor inlet end 1; Remain on 1200-1500 ℃ to the temperature of the combustion zone 3 of reactor with the reactor intensification and with temperature adjustment steam; The about 6-9 of gas discharge ton/time, the about 20000-25000NM of oxygen
3In/time, reactor adopts the structure of embodiment 3, reaction zone 4 internal diameter 1.2-1.5 rice, reaction head of district 5-6 rice;
3) feed naphtha after the preheating gasification with spray regime through the raw material nozzles 6 of reactor with 124 tons/time flow get into reactor; Be warming up to suitable cracking temperature 860-900 ℃ with quick contact of high-temperature flue gas that the combustion zone produces; The control of cracking temperature is by fuel flow rate, temperature adjustment steam and the adjustment of cracking stock flow tandem; Reaction pressure is at 0.2-0.3MPa, and the time of staying is in 0.1-0.2 second, but the composition reference table 1 of product;
4) cracking gas that generates of reaction directly gets into quenching boilers through the product outlet 7 of said reactor and is cooled to below 500 ℃, stopping secondary response and to reclaim heat of high temperature, and then (sloughs water, CO simultaneously through quenching unit, compression unit
2And sour gas), cryogenic unit and separative element are handled the final low-carbon alkene that obtains the polymer grade quality in back;
5) step 4) separated hydrogen and methane are returned step 2 through pipeline), acting as a fuel gets into reactor through fuel and oxygen jet 5, substitutes the initial natural gas that uses gradually; The heat that quenching boiler reclaims is used to take place high steam and supplies full factory to use.
Claims (14)
1. a reactor that is used for preparing low-carbon olefins by cracking reactions is characterized in that: have the arrival end (1) and the port of export (2), and these two ends are in relative position on reactor; Inside reactor is combustion zone (3) from 1/4 space of arrival end, and its complementary space is reaction zone (4); Said arrival end (1) is provided with fuel and the oxygen jet (5) that leads to combustion zone (3), and the port beyond this nozzle seals; On the sidewall of reactor between said combustion zone (3) and the reaction zone (4), be provided with raw material nozzles (6), the said port of export (2) is provided with product outlet (7); Described fuel and oxygen jet (5) and raw material nozzles (6) are one or more nozzle arrangements.
2. the described reactor of claim 1, it is characterized in that: the internal diameter of the arrival end of said reactor (1) and the port of export (2) is less than the internal diameter of reaction zone (4).
3. the described reactor of claim 2, it is characterized in that: said arrival end (1) inside is variable-diameter structure.
4. the described reactor of claim 3, it is characterized in that: said arrival end (1) inside is the venturi type variable-diameter structure.
5. the described reactor of claim 1, it is characterized in that: said reaction zone (4) inside is provided with flow restriction (8).
6. the described reactor of claim 5, it is characterized in that: described flow restriction (8) is the current limiting plate of some axial distribution.
7. the described reactor of claim 1 is characterized in that: be provided with temperature adjustment steam inlet (9) in the middle part of described combustion zone (3); Described combustion zone (3) outer wall is provided with cooling device (10).
8. the described reactor of claim 7, it is characterized in that: described cooling device (10) is cooling jacket, interlayer or coil pipe.
9. method of utilizing the described reactor of claim 1 through preparing low-carbon olefins by cracking reactions may further comprise the steps:
1) preheating cracking stock to 150～700 ℃;
2) let fuel and oxygen burn the CO of generation through the fuel of said reactor and the combustion zone of oxygen jet (5) entering reactor according to the ratio of completing combustion
2, H
2O and flue-gas temperature remain on 1000～1500 ℃;
3) step 1) is handled the flow of feed gas that obtains and is got into described reactor through the raw material nozzles (6) of said reactor; With step 2) the quick contact heat-exchanging of high-temperature gas that produces of burning; Raw material is warming up to 800～1000 ℃ rapidly and carries out cracking reaction; The cracking reaction time is 0.1-0.3 second, and reaction pressure contains low-carbon alkene, methane, hydrogen and other byproducts at 0.1-0.5MPa in the cracking gas that reaction generates;
4) the product cracking gas that generates of the reaction of step 3) directly gets into cooling device through the product outlet (7) of said reactor and is cooled to below 500 ℃; Stopping secondary response and to reclaim heat of high temperature, and then finally obtain the low-carbon alkene of polymer grade quality through over-quenching, compression, deep cooling and separating step; Also need carry out purified treatment, i.e. acid gas removal body and water in the described compression process.
10. the described method for preparing low-carbon alkene of claim 9, it is characterized in that: the described cracking stock of step 1) comprises lighter hydrocarbons, naphtha, light diesel fuel cut, heavy diesel fuel cut, hydrogenation tail oil or heavy oil.
11. the described method for preparing low-carbon alkene of claim 9 is characterized in that: step 2) described fuel is gaseous fuel or liquid fuel.
12. the described method for preparing low-carbon alkene of claim 11, it is characterized in that: described gaseous fuel is selected from ethane, propane, ethane and propane mixture or natural gas; Described liquid fuel is selected from ethanol, diesel oil or gasoline.
13. the described method for preparing low-carbon alkene of claim 9 is characterized in that: the described preheating of step 1) is through heat exchanger or heating furnace heating; Step 2) high-temperature flue-gas that generates of said fuel and oxygen combustion carries out dual regulation through the mode that the control fuel flow rate combines to feed temperature adjustment steam.
14. the described method for preparing low-carbon alkene of claim 9 is characterized in that: isolated methane of the described separating step of step 4) and hydrogen as fuel are got back to step 2 once more) reactor cycles use; Isolated other byproducts of the described separating step of step 4) are got back to step 1) once more as raw material carry out preheating.
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| CN 201010284541 CN101920187B (en) | 2010-09-17 | 2010-09-17 | Equipment and method for preparing low-carbon olefins by cracking reactions |
| PCT/CN2010/077759 WO2012034295A1 (en) | 2010-09-17 | 2010-10-15 | Apparatus and method for preparing lower olefin by cracking reaction |
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| CN 201010284541 CN101920187B (en) | 2010-09-17 | 2010-09-17 | Equipment and method for preparing low-carbon olefins by cracking reactions |
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| DE102014203043B3 (en) * | 2014-02-19 | 2015-03-05 | Minimax Gmbh & Co. Kg | Löschfluiddüsensystem, in particular extinguishing gas nozzle system for stationary fire extinguishing systems, as well as extinguishing fluid nozzle and -blende for selbiges |
| CN106675651B (en) * | 2016-12-26 | 2020-01-17 | 赛鼎工程有限公司 | Method and equipment for producing gasoline by biomass gasification |
| CN110283628A (en) * | 2019-07-10 | 2019-09-27 | 北京石油化工工程研究院 | A kind of cracking gasification reactor |
| CN110607181A (en) * | 2019-10-24 | 2019-12-24 | 上海齐耀热能工程有限公司 | Equipment and method for preparing light hydrocarbons by pressurizing and directly heating cracking |
| WO2022010821A1 (en) | 2020-07-06 | 2022-01-13 | Sabic Global Technologies B.V. | Reactor system for the production of high value chemical products |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2063292A (en) * | 1979-11-13 | 1981-06-03 | Rockwell International Corp | Method of producing olefins from hydrocarbons |
| CN2687128Y (en) * | 2003-10-17 | 2005-03-23 | 中国科学院过程工程研究所 | Cracking gasification furnace for clean preparing low carbon olefin such as ethylene |
| CN1751009A (en) * | 2003-02-18 | 2006-03-22 | 英诺文尼欧洲有限公司 | Auto thermal cracking reactor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3116343A (en) * | 1960-08-19 | 1963-12-31 | Shell Oil Co | Temperature-stabilized conversion of hydrocarbons and the like |
| US3498753A (en) * | 1966-07-04 | 1970-03-03 | Nippon Zeon Co | Apparatus for thermal cracking of hydrocarbon |
| DE1643811A1 (en) * | 1966-10-14 | 1971-03-11 | Chepos Zd Y Chemickeho A Potra | Process and system for carrying out pyrolysis reactions |
| JPS4873402A (en) * | 1971-12-29 | 1973-10-03 | ||
| CN1259391C (en) * | 2003-10-17 | 2006-06-14 | 中国科学院过程工程研究所 | Method of cracking heavy hydrocarbon to prepare low-carbon olefin and the cracking gasifier system |
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2010
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- 2010-10-15 WO PCT/CN2010/077759 patent/WO2012034295A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2063292A (en) * | 1979-11-13 | 1981-06-03 | Rockwell International Corp | Method of producing olefins from hydrocarbons |
| CN1751009A (en) * | 2003-02-18 | 2006-03-22 | 英诺文尼欧洲有限公司 | Auto thermal cracking reactor |
| CN2687128Y (en) * | 2003-10-17 | 2005-03-23 | 中国科学院过程工程研究所 | Cracking gasification furnace for clean preparing low carbon olefin such as ethylene |
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| WO2012034295A1 (en) | 2012-03-22 |
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Effective date of registration: 20230810 Address after: Room 2105, Building 4, Lihong Garden, No. 6 Zuojiazhuang Middle Street, Chaoyang District, Beijing, 100028 Patentee after: Wang Zhonghua Patentee after: Wang Zhouhui Patentee after: Wang Ning Address before: Room 2105, Building 4, Lihong Garden, No. 6 Zuojiazhuang Middle Street, Chaoyang District, Beijing, 100028 Patentee before: Wang Zhonghua Patentee before: Lin Yuerong |