CN1228290C - Method for preapring benzo cyclonbutene from benzo cyclopent sulfone high-temperature catalytic cracking - Google Patents
Method for preapring benzo cyclonbutene from benzo cyclopent sulfone high-temperature catalytic cracking Download PDFInfo
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- CN1228290C CN1228290C CN 03129463 CN03129463A CN1228290C CN 1228290 C CN1228290 C CN 1228290C CN 03129463 CN03129463 CN 03129463 CN 03129463 A CN03129463 A CN 03129463A CN 1228290 C CN1228290 C CN 1228290C
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Abstract
The present invention relates to a method for preparing benzo cyclonbutene from benzo cyclopentyl sulphone through high temperature catalytic cracking. Nickel-chrome alloy metal wires are added as catalysts into a cracking device, the average productive rate of benzo cyclonbutene monomers prepared by thermal cracking can reach 95%, and the content of benzo cyclonbutene monomers in products reaches 98%. The productive quantity of benzo cyclonbutene monomers is increased greatly, and after-treatment refining technology is simplified.
Description
Technical field
The present invention relates to a kind of preparation method of monomer benzocyclobutene, more specifically to a kind of be raw material with benzo ring penta sulfone, prepare the method for benzocyclobutene by the high-temperature catalytic cracking.
Technical background
The low-dielectric loss macromolecular material is widely used in aspects such as electric insulation, saturating ripple, and at present used material dielectric constant height, dielectric loss are big, thermotolerance is not high, does not satisfy the application requiring that requires extra high occasion, as high-density multi-layered printed circuit board (PCB) etc.And the benzocyclobutene material is the first-selected organic materials that can satisfy these requirements, its dielectric properties excellence (specific inductivity 2.7, dissipation factor 0.0008), and water-intake rate low (boiling water 24h only 0.25%), the coefficient of expansion is low; Its forming process ratio is easier to, and do not emit low molecular product during polymerization, curing speed is fast, performances such as and available several different methods solidifies, and is heat-resisting are better than resins such as BMI, PMR, epoxy, cyanate, therefore can be used to make extensive IC printed board, advanced electronics, navigational material, even the advanced composite material member, as saturating wave antenna window of top grade or cover etc., can be widely used in high-tech sector.
Benzocyclobutene is the basic raw material monomer of polyphenyl and cyclobutene engineering materials.Benzo ring penta sulfone (1,3-dihydroisothianaphthen-2,2-dioxide) to prepare benzocyclobutene (Benzocyclobutene is called for short BCB) monomer be one of main method of benzocyclobutene monomer preparation to thermo-cracking.As far back as 1958, it was the method that the raw material thermo-cracking prepares the monomer benzocyclobutene with benzo ring penta sulfone that Cavah and Deana disclose a kind of in document (J.Amer.Chem.Soc.1958,81,4266), but the productive rate of benzocyclobutene only is 65%; Nineteen sixty-five, Oliver and Ongley improve aforesaid method in document (Chem.Ind, 1965, June, 12,1024), and the average yield of benzocyclobutene is brought up to 74%.In a word, because simple thermo-cracking benzo ring penta sulfone can't further reduce the generation of by product, therefore the average yield of the benzocyclobutene of prior art is all lower, this has not only caused raw-material waste, and aftertreatment treating process (obtaining pure benzocyclobutene monomer) results in hand cramps, and makes the yield of final purified petroleum benzin and cyclobutene lower.Therefore, branch of industry wishes that the relevant works technician provides a kind of new method, can increase substantially the productive rate of benzocyclobutene, satisfies the modern high technology requirement growing to material.
Summary of the invention
The objective of the invention is to prepare the technical defective of benzocyclobutene in order to overcome benzo ring penta sulfone Pintsch process, the method that a kind of benzo ring penta sulfone high-temperature catalytic cracking prepares benzocyclobutene has been proposed, the productive rate of benzocyclobutene is reached more than 95%, and the content of benzocyclobutene monomer reaches about 98% in the product.Thereby improved the output of benzocyclobutene monomer greatly, can satisfy the requirement of branch of industry.
Design of the present invention is such:
The process that the penta sulfone cracking of benzo ring prepares benzocyclobutene is a process of taking off sulfone Cheng Huan, its scission reaction mechanism be benzo ring penta sulfone add under certain condition the adjacent quinoline of thermosetting the intermediate of structure or diradical structure, take off the sulfone reaction.The intramolecular cyclization of diradical promptly forms benzocyclobutene; The diradical dimerization reaction then forms dimer 1,2,5,6-benzo cyclooctadiene; In addition, the diradical intermediate can also generate other products, as o-Xylol etc.In addition, the benzocyclobutene of generation is also unstable, and open loop again more at high temperature forms dimer etc., and its reaction process is shown in following equation:
The scission reaction of ideal benzo ring penta sulfone should be to impel the generation of product benzocyclobutene, restriction by product 1,2,5, the generation of 6-benzo cyclooctadiene and other compounds.Simultaneously, prevent the benzocyclobutene open loop again that generated.
For this reason, the contriver has carried out long-term exploration in experimental installation, seeks the above-mentioned desirable catalyzer that requires that conforms to that a class obtains easily, and under certain conditions, but its specificity ground makes benzo ring penta sulfone cracking generation benzocyclobutene.
The present invention is achieved in that
The contriver is by secular experiment screening; in tubular type heat scission reaction stove (hereinafter to be referred as tube cracking furnace); add the nickel-chromium alloy silk that commercially available model is Cr20Ni80 or Cr15Ni60 model; it can make coil spring shape; be packed in the heating interval of silica tube in the tube cracking furnace; under the condition of negative pressure, protection of inert gas, feed benzo ring penta sulfone through the preheating gasification.Furnace temperature can be regulated and control in 550～750 ℃ of scopes in the tube cracking furnace, and under certain condition, benzo ring penta sulfone can generate benzocyclobutene by specificity ground catalytic pyrolysis.
Above catalytic pyrolysis process is to carry out on the surface of silica tube inner catalyst, and catalyst consumption is that every gram benzocyclobutene use surface-area is 5～14cm
2Catalyzer; When tube cracking furnace starts, taking by weighing a certain amount of benzo ring penta sulfone crystal earlier packs in the gasifier, vacuumize the pressure that makes in the cracker and drop to 0.05mmHg, gently feed rare gas element then, make system pressure remain on 10mmHg following (vacuum tightness maintains more than the 750mmHg).Rare gas element is first elected high purity nitrogen, also can use argon gas.Silica tube places pyrolyzer, pyrolyzer adopts the resistance wire heating, make temperature in the tube cracking furnace by the automatic instrument(s) regulation and control, guarantee that temperature (or catalyst surface temperature) can be chosen 550～750 ℃ of scopes in the silica tube, to investigate catalytic pyrolysis effect under the differing temps.Gasifier heats with electric food warmer (or bowl), when temperature in the gasifier reaches 280 ℃ of left and right sides, the benzo ring penta sulfone gasification of fusing enters in the cracking silica tube, contact with (in 550～750 ℃ of scopes) catalyst surface in the high-temperature zone, carry out single-minded catalytic cracking reaction fast, the material that splitting gas participates in the scission reaction process in other words was controlled in 0.1～0.7 second in the residence time of silica tube high-temperature zone, benzocyclobutene generates the back and passes through the silica tube high-temperature zone rapidly with the rare gas element carrier band under high vacuum, enter the cooling of secondary cold-trap, collect the benzocyclobutane ene product.The outward appearance of product is the glassy yellow oily liquid.The cooling agent of cold-trap can be liquid nitrogen, also can be dry ice-propanone.In the above cracking process, splitting gas also is the key that concerns productive rate in the residence time of high-temperature zone, time has lacked phenylpropyl alcohol ring penta sulfone and has had little time to transform, time has been grown the tendency that the benzocyclobutene that generates has reverse generation by product, therefore, to participate in the most optimal retention time of material in the silica tube high-temperature zone of scission reaction process in other words be 0.2～0.5 second to splitting gas.
The contriver finds from experiment:
Improve the catalytic pyrolysis temperature, the cracking transformation efficiency of benzo ring penta sulfone is also high more.Owing in cracking process, mainly exist the intramolecular cyclization reaction of generation benzocyclobutene and the dimerization reaction of two free radical intermediates, the former is thermo-negative reaction, the latter is thermopositive reaction, improves cracking temperature and helps intramolecular cyclization reaction generation product benzocyclobutene.So, improve the catalytic pyrolysis temperature, help scission reaction and carry out to the direction that generates benzocyclobutene.But when cracking temperature is too high (as more than＞800 ℃ the time), if do not change splitting gas in the high-temperature zone residence time, more serious carbonization phenomenon takes place then, the blackening of crude product color, quantity is fewer and feweri.So the temperature Ying Yi of catalytic pyrolysis is chosen in 550～750 ℃ of scopes, is good with 630～670 ℃.
Splitting gas also is an important factor of decision cracking benzocyclobutene yield in the residence time of high-temperature zone.Splitting gas is too short in the residence time of Pintsch process section, and benzo ring penta sulfone has little time complete cracking conversion and just leaves cracker, and the content of benzocyclobutene is not high in the product; Splitting gas then makes the benzocyclobutane ene product of reaction and generation continue ring-opening reaction takes place under hot conditions at Pintsch process section overstand, and dimer content is increased.Experiment shows that splitting gas should be the best with 0.2～0.5 second in the residence time of high temperature section between 0.1～0.7 second.After the free air delivery of vacuum pump was selected, the length decision splitting gas of Pintsch process section was in the residence time of high-temperature zone.Vacuum pump with 120 liters of/minute discharge capacities is an example, and selecting internal diameter for use is 30 millimeters crystalline silica cracking tube, and its length is 600～1800 millimeters is advisable, with 1200 millimeters the bests.Improve the exhaust capacity of vacuum pump, in constant device cracking section, can regulate and control the residence time of splitting gas, reaction is carried out towards the direction that helps improving target product in high temperature section.In this device, the free air delivery of vacuum pump can increase to 240 liters/minute or higher.
Shown in this clearly demarcated design partial reaction equation, benzo ring penta sulfone add under certain condition the adjacent quinoline of thermosetting the intermediate of structure or diradical structure, take off the sulfone reaction.The intramolecular cyclization of diradical promptly forms benzocyclobutene; The diradical dimerization reaction then forms dimer 1,2,5,6-benzo cyclooctadiene.Here the former is a unimolecular reaction, and the latter is a dimolecular reaction, in addition benzocyclobutene again open loop to form dimer also be dimolecular reaction.If the vacuum tightness of system strengthens, the concentration of splitting gas is thinning, and the chance of intermolecular collision diminishes, and helps unimolecular reaction.Therefore, cracking process must be chosen to be under certain vacuum degree condition and carries out.Its cracking pressure is between 2～20mmHg, should be to carry out under 2～10mmHg at cracking pressure.Consider that cracking process uses rare gas element and protect, the existence of rare gas element also helps reducing the chance of intermolecular collision, so the cracking pressure during cracking can be controlled at 10mmHg.If select for use the free air delivery of vacuum pump bigger, can consider to strengthen the flow of rare gas element.Under the condition of condition of high vacuum degree, high inert gas flow, catalytic cracking reaction more helps the generation of target product.
Description of drawings
Further specify content of the present invention below in conjunction with accompanying drawing.
Fig. 1 prepares the device synoptic diagram of benzocyclobutene through the high-temperature catalytic cracking for benzo ring penta sulfone
Wherein: 1---heating kettle (being electric heating Pans or title Electric heating bowl);
2---gasifier (0.5L), interior dress raw material benzo ring penta sulfone;
3---tube cracking furnace, a kind of horizontal pipe pyrolyzer;
4---catalyzer, the catalyzer that nickel one chromium alloy wire of interior dress coil spring shape constitutes; The external diameter of nickel-chromium alloy silk is 0.2～0.5mm, and the quantity of catalyzer is according to 5～14cm
2/ gBCB is provided with;
5---crystalline silica cracking tube;
6---cold-trap 1
#, the cooling agent of adorning in the chuck is liquid nitrogen or dry ice-propanone;
7---cold-trap 2
#, the cooling agent of adorning in the chuck is liquid nitrogen or dry ice-propanone.
More than install the cracking job step:
1, device adds earlier raw material benzo ring penta sulfone in gasifier (2) before startup, installs then whole Device makes it to be in good sealing state;
2, open vacuum system until the pressure in the cracker drops to below the 0.05mmHg, then gently logical Enter inert gas, make system pressure remain on 10mmHg following (more than the 750mmHg vacuum), Inert gas can be high pure nitrogen or argon gas, is advisable with High Purity Nitrogen from cheap and easy to get.
3, open tube cracking furnace (3), at control instrument the cracking temperature of tube cracking furnace is set, make pipe The formula pyrolysis furnace reaches predetermined cracking temperature and keeps stable;
4, open electric food warmer (1), the interior temperature of gasifier (2) is reached about 280 ℃, fusing in the gasifier Benzo ring penta sulfone gasification enter in the cracking silica tube (5), with (550～750 in the high-temperature region In ℃ scope) catalyst (4) Surface Contact, carry out fast single-minded catalytic cracking reaction;
5, the product of catalytic pyrolysis enters in the cold-trap (6,7) quilt with the inert gas thermal treatment zone that speeds away Cooling is caught, and namely gets the semifinished product benzocyclobutene.
Because the subtractive process of benzocyclobutene is mature technology, have special document to discuss, so among the present invention to benzene And the narration of the process for purification of cyclobutane is omitted. But must be pointed out, because in the product that method of the present invention obtains The content of benzocyclobutene is higher, and accessory substance is less, so the post-processing step of subtractive process is comparatively easy.
In addition, also must be pointed out: method of the present invention not only can adopt horizontal pipe cracking as shown in Figure 1 Device also can adopt vertical pipe cracker (not shown), can reduce floor space like this, for Its principle of vertical pipe cracker and horizontal pipe cracker are in full accord, but should notice guaranteeing that catalyst fills Full whole Pintsch process zone, the details on its apparatus structure no longer describes in detail here.
Further illustrate content of the present invention below in conjunction with example, but these examples do not limit protection scope of the present invention.
Embodiment
Embodiment 1
Cracking condition:
Cracking temperature: 650 ± 10 ℃;
Cracking vacuum tightness: 750mmHg (is a cracking pressure: 10mmHg);
Vacuum pump free air delivery 120L/min;
Cracking tube size: φ 30 * 1200mm (external diameter is 35, internal diameter is 30 silica tube);
Catalyzer: Cr15Ni60 type nickel-chromium alloy silk, catalyst surface area is 200cm
2
In the device that Fig. 1 shows, the cracking section of silica tube places in the pyrolyzer, and pyrolyzer adopts the resistance wire heating, and temperature is controlled at 650 ± 10 ℃.Taking by weighing 30 gram benzo rings, penta sulfone crystal packs in the gasifier.Vacuumize the pressure that makes in the cracker and drop to 0.05mmHg, gently feed purity nitrogen then, make system pressure remain on 10mmHg (750mmHg vacuum tightness).Gasifier heats with electric food warmer, and when temperature in the gasifier reached 280 ℃ of left and right sides, the gasification of benzo ring penta sulfone of fusing entered silica tube cracking section.Put into the nickel-chromium alloy silk as catalyzer in the silica tube cracking section, modes of emplacement adopts coil spring shape, and the placement scope relates to whole high-temperature catalytic cracking zone.Benzo ring penta sulfone of gasification is through after the cracking of catalyst surface high-temperature catalytic, and split product is collected by the cooling of secondary cold-trap, and it is liquid nitrogen that the cooling agent of cold-trap adopts.The outward appearance of product is the oily liquid of yellow transparent, product quantity 17.5 grams, and gas chromatographic analysis is benzocyclobutene content wherein: 85.1%, calculate thus, the productive rate of benzocyclobutene should be 80.2%, and every gram benzocyclobutene usable floor area is 13.43cm
2Catalyzer.
Embodiment 2
Cracking condition:
Cracking temperature: 650 ± 10 ℃;
Cracking vacuum tightness: 750mmHg (is a cracking pressure: 10mmHg);
Vacuum pump free air delivery 120L/min;
Cracking tube size: φ 30 * 1200mm (with embodiment 1);
Catalyzer: Cr20Ni80 type nickel-chromium alloy silk, the surface-area of catalyzer is 108cm
2
In cracker shown in Figure 1, silica tube cracking section places in the pyrolyzer, and pyrolyzer adopts the resistance wire heating, and temperature is controlled at 650 ± 10 ℃.Taking by weighing 30 gram benzo rings, penta sulfone crystal packs in the gasifier.Vacuumize the pressure that makes in the cracker and drop to 0.05mmHg, gently feed purity nitrogen then, make system pressure remain on 10mmHg (750mmHg vacuum tightness).Gasifier heats with electric food warmer, and when temperature in the gasifier reached 280 ℃ of left and right sides, the gasification of benzo ring penta sulfone of fusing entered silica tube cracking section.Put into the nickel-chromium alloy silk as catalyzer in the silica tube cracking section, modes of emplacement adopts coil spring shape, and the placement scope relates to whole high-temperature catalytic cracking zone.Benzo ring penta sulfone of gasification is through after the cracking of catalyst surface high-temperature catalytic, and split product is collected by the cooling of secondary cold-trap, and it is liquid nitrogen that the cooling agent of cold-trap adopts.The outward appearance of product is the oily liquid of yellow transparent, product quantity 18.0 grams, and gas chromatographic analysis is benzocyclobutene content wherein: 92.0%, calculate thus, the productive rate of benzocyclobutene should be 89.2%, and every gram benzocyclobutene usable floor area is 6.52cm
2Catalyzer.
By embodiment 1～2 as seen:
(1) under the condition that catalyzer exists, the productivity ratio prior art of benzocyclobutene is significantly improved;
(2) catalyzer Gr20Ni80 is than GR15Ni60 excellent catalytic effect not only, and consumption is few.
Embodiment 3
Cracking condition:
Cracking temperature: 650 ± 10 ℃;
Cracking vacuum tightness: 758mmHg (promptly installing internal pressure 2mmHg);
Vacuum pump free air delivery 240L/min;
Cracking tube size: φ 30 * 1800mm (φ 30 is cracking silica tube internal diameter);
Catalyzer: Cr20Ni80 type nickel-chromium alloy silk, the surface-area of catalyzer is 200cm
2
In cracker shown in Figure 1, silica tube cracking section places in the pyrolyzer, and pyrolyzer adopts the resistance wire heating, and temperature is controlled at 650 ± 10 ℃.Taking by weighing 30 gram benzo rings, penta sulfone crystal packs in the gasifier.Vacuumize the pressure that makes in the cracker and drop to 0.05mmHg, gently feed argon gas then, make system pressure remain on 2mmHg (758mmHg vacuum tightness).Gasifier heats with electric food warmer, and when temperature in the gasifier reached 280 ℃ of left and right sides, the gasification of benzo ring penta sulfone of fusing entered silica tube cracking section.Put into the nickel-chromium alloy silk as catalyzer in the silica tube cracking section, modes of emplacement adopts coil spring shape, and the placement scope relates to whole high-temperature catalytic cracking zone.Benzo ring penta sulfone of gasification is through after the cracking of catalyst surface high-temperature catalytic, and split product leaves the Pintsch process district with rare gas element immediately, enters the cooling zone and is collected by the cooling of secondary cold-trap, and it is liquid nitrogen that the cooling agent of cold-trap adopts.The outward appearance of product is the oily liquid of yellow transparent, product quantity 18.0 grams, and gas chromatographic analysis is benzocyclobutene content wherein: 98.0%, calculate thus, the productive rate of benzocyclobutene should be more than 95%, and every gram benzocyclobutene usable floor area is 11.34cm
2Catalyzer.
Embodiment 4
Cracking condition:
Cracking temperature: 560 ± 10 ℃;
Cracking vacuum tightness: 750mmHg (is a cracking pressure: 10mmHg);
Vacuum pump free air delivery 120L/min;
Cracking tube size: φ 30 * 1200mm (φ 30 is the silica tube internal diameter);
Catalyzer: Cr20Ni80 type nickel-chromium alloy resistance wire, the surface-area of catalyzer is 108cm
2
In cracker shown in Figure 1, silica tube cracking section places in the pyrolyzer, and pyrolyzer adopts the resistance wire heating, and temperature is controlled at 560 ± 10 ℃.Taking by weighing 30 gram benzo rings, penta sulfone crystal packs in the gasifier.Vacuumize the pressure that makes in the cracker and drop to 0.05mmHg, gently feed purity nitrogen then, make system pressure remain on 10mmHg (750mmHg vacuum tightness).Gasifier heats with electric food warmer, and when temperature in the gasifier reached 280 ℃ of left and right sides, the gasification of benzo ring penta sulfone of fusing entered silica tube cracking section.Put into the nickel-chromium alloy silk as catalyzer in the silica tube cracking section, modes of emplacement adopts coil spring shape, and the placement scope relates to whole high-temperature catalytic cracking zone.Benzo ring penta sulfone of gasification is through after the cracking of catalyst surface high-temperature catalytic, and split product is collected by the cooling of secondary cold-trap, and it is liquid nitrogen that the cooling agent of cold-trap adopts.The outward appearance of product is the oily liquid of yellow transparent, product quantity 18.0 grams, and gas chromatographic analysis is benzocyclobutene content wherein: 83.5%, calculate thus, the productive rate of benzocyclobutene should be 81%, and every gram benzocyclobutene usable floor area is 7.18cm
2Catalyzer.
By embodiment 4 as seen: even under low catalytic pyrolysis temperature (560 ± 10 ℃), use catalyzer of the present invention, the productivity ratio prior art of target product benzocyclobutene still increases about 10%.As seen catalytic pyrolysis has marked improvement than simple thermo-cracking.
Embodiment 5
Cracking condition:
Cracking temperature: 750 ± 10 ℃;
Cracking vacuum tightness: 750mmHg (is a cracking pressure: 10mmHg);
Vacuum pump free air delivery 120L/min;
Cracking tube size: φ 30 * 1200mm (φ 30 is the silica tube internal diameter):
Catalyzer: Cr20Ni80 type nickel-chromium alloy silk, the surface-area of catalyzer is 108cm
2
In cracker shown in Figure 1, silica tube cracking section places in the pyrolyzer, and pyrolyzer adopts the resistance wire heating, and temperature is controlled at 750 ± 10 ℃.Taking by weighing 30 gram benzo rings, penta sulfone crystal packs in the gasifier.Vacuumize the pressure that makes in the cracker and drop to 0.05mmHg, gently feed purity nitrogen then, make system pressure remain on 10mmHg (750mmHg vacuum tightness).Gasifier heats with electric food warmer, and when temperature in the gasifier reached 280 ℃ of left and right sides, the gasification of benzo ring penta sulfone of fusing entered silica tube cracking section.Put into the nickel-chromium alloy silk as catalyzer in the silica tube cracking section, modes of emplacement adopts coil spring shape, and the placement scope relates to whole high-temperature catalytic cracking zone.Benzo ring penta sulfone of gasification is through after the cracking of catalyst surface high-temperature catalytic, and split product is collected by the cooling of secondary cold-trap, and it is liquid nitrogen that the cooling agent of cold-trap adopts.The outward appearance of product is the transparent oily liquid of yellow black, product quantity 16.0 grams, and gas chromatographic analysis is benzocyclobutene content wherein: 85.7%, calculate thus, the productive rate of benzocyclobutene should be 73.8%, and every gram benzocyclobutene usable floor area is 7.87cm
2Catalyzer.
By embodiment 5 as seen:
(1) the catalytic pyrolysis temperature is brought up to 750 ± 10 ℃, does not help the raising of the productive rate of target product benzocyclobutene, and the decline of the quality of product, because high-temperature lower part is divided raw material and split product generation carbonization:
(2) experiment is found: improve the catalytic pyrolysis temperature, the carbon coking occurs at the part catalyst surface, this result is unfavorable for the catalytic pyrolysis of material subsequently very much.Therefore, the contriver recommends best catalytic pyrolysis process to carry out in 630～670 ℃ of scopes.
Claims (5)
1, a kind ofly prepare the method for benzocyclobutene by benzo ring penta sulfone through the high-temperature catalytic cracking, said high-temperature catalytic cracking ties up under negative pressure and the protection of inert gas to be carried out, and the condition when it is characterized in that the high-temperature catalytic cracking is:
(1) cracking temperature is 550～750 ℃;
(2) cracking pressure is 2～20mmHg;
(3) rare gas element is high purity nitrogen or argon gas;
(4) catalyzer is commercially available Cr15Ni60 or Gr20Ni80 type nickel-chromium alloy silk;
(5) catalyst consumption is that every gram benzocyclobutene use surface-area is 5～14cm
2Catalyzer;
(6) splitting gas is 0.1～0.7 second in the cracking high-temperature zone residence time.
2, the method for claim 1 is characterized in that, wherein said cracking temperature is 630～670 ℃.
3, the method for claim 1 is characterized in that, the pressure during wherein said cracking is 2～10mmHg.
4, the method for claim 1 is characterized in that, wherein said splitting gas is 0.2～0.5 second in the cracking high-temperature zone residence time.
5, the method for claim 1, it is characterized in that described high-temperature catalytic scission reaction process horizontal pipe cracking dress p put or vertical tubular type cracker in carry out.
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