CN1696249A - Directional reactive catalysis thermal cracking method for direct converting low carbon alkane without need of oxygen - Google Patents
Directional reactive catalysis thermal cracking method for direct converting low carbon alkane without need of oxygen Download PDFInfo
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Abstract
A directional catalytic thermocracking reaction for non-oxygen direct conversion of low-carbon alkane includes reaction between the preheated heavy petroleum hydrocarbon and hot cracking catalyst from the first generator in the first reactor to obtain the oil gas and carbon deposited catalyst, stripping the catalyst, regenerating in the first generator, delivering the oil gas in the following product separation system, feeding low-carbon alkane in the second reactor, reacting on the aromatizing catalyst from the second regenerator to obtain arylhydrocarbon and H2, regenerating the catalyst, and separating arylhydrocarbon from H2.
Description
Technical Field
The invention belongs to a directional reaction catalytic thermal cracking method for directly converting low-carbon alkane without oxygen, and particularly relates to a process method for combining aromatization of low-carbon alkane and catalytic thermal cracking of hydrocarbon oil.
Background
For the modern petrochemical industry, ethylene and propylene are the most important basic raw materials. The world 98% of ethylene production processes are tubular furnace steam cracking. Because the steam cracking temperature is very high and the requirements on the material are very strict, the overall investment of the device is very high, and the furnace tube of the cracking furnace is easy to coke, so the raw material only needs to use light raw materials such as natural gas, naphtha or light diesel oil, and the production cost is high.
As crude oil becomes increasingly heavier, the sources of light feedstocks for ethylene production by steam cracking are limited, and attention has been directed to processes for producing ethylene from heavy oils. At present, the heavy oil is generally hydrocracked to obtain light fraction or hydrocracked tail oil is used as a raw material for producing ethylene by using the heavy oil as the raw material, and then the heavy oil is fed into a tubular furnace for thermal cracking, so that the investment is more expensive.
SU1243812 is a process for preparing ethylene by catalytic cracking developed in Russia. The process uses potassium vanadate catalyst with ceramic as carrier, and in addition, coking inhibitor is added. The semi-industrial experimental scale is 2000Kg/h, the cracking temperature is 780-790 ℃, the retention time is 0.1-0.2 s, the ethylene yield is 34.5%, and the propylene yield is 17.5%.
DD233584 and DD2243708 are TCSC catalytic cracking technologies studied in Germany. The technology consists of thermal cracking catalyst, AGO and VGO thermal catalytic conversion technology.
Hei 6-346062 is a catalytic cracking technique for the formation of Asahi Japan: a low temperature catalyst was developed for use at 680 c. The catalyst is mesoporous zeolite, the ratio of silicon to aluminum is 50-300, the granularity is 0.01-1.0 um, the pore diameter is 0.5-0.65 nm, and the zeolite is ZSM-5 or ZSM-11.
JP18902 is a catalytic cracking technique using an alkali metal oxide of lithium as a catalyst. The naphtha used in the technology is used as a raw material and can be used at 600 ℃.
USP4579997, USP4621163 and CN103900 are catalytic cracking technologies using light hydrocarbon as raw material.
The above-mentioned techniques for producing olefins using heavy raw materials, inert solids such as silica sand or coke as heat carriers or alkali metals or alkali metal oxides as catalysts have high reaction temperatures, and have not been industrially applied.
CN1069016A and CN1215041A are heavy oil direct contact cracking (HCC) process technologies introduced by the Chinese petrochemical Luoyang engineering company for the reference of heavy oil catalytic cracking technology and experience. The technology has wide raw material sources, can use various cracking raw materials, and is particularly suitable for cracking straight run wax oil, residual oil, coking wax oil, thermal cracking heavy oil, DAO and other secondary processing oil. Under the reaction temperature of 700-750 ℃, the single-pass yield of ethylene is 19-27% and the yield of ethylene, propylene and butylene is over 50% by using a special catalyst for LCM-5. The process has been complied with by 80kt/a industrial equipment.
CN1083092A, CN1218786A, CN1221015A and CN1222558A are new processes for preparing ethylene and propylene from heavy oil developed by petrochemical engineering scientific research institute, namely catalytic thermal Cracking (CPP) process. The process is based on the traditional catalytic cracking device technology, takes heavy oil as a raw material, adopts a novel special catalyst for catalytic thermal cracking (CFP molecular sieve catalyst), and produces ethylene and propylene under the condition of much lower temperature than steam cracking temperature. Laboratory bench and pilot scale studies have made breakthrough progress. Under specific process conditions, a novel catalyst special for catalytic thermal cracking is adopted, 30% of Daqing wax oil doped with slag reduction is used as a raw material, the ethylene yield can reach 23-24%, the propylene yield is about 15%, and the total yield of triene is 46-47% under the conditions of 620-640 ℃ of reaction temperature, 0.07-0.10 MPa of reaction pressure, 25 catalyst-oil ratio, 2s of reaction time and 50% of water injection. The CPP process is based on the traditional fluid catalytic cracking technology, and is favorable for industrial application of the process on the basis of new design or modification of an original catalytic cracking device by mature catalytic cracking technology design experience, design method and abundant operation experience. In addition, the CPP technology fully utilizes the catalytic action of the catalyst according to the characteristics of free radical reaction and carbonium ion reaction, gives consideration to the production of propylene besides the production of ethylene, and can flexibly produce ethylene or propylene according to the market demand through the adjustment of the formula and the operation condition of the catalyst. The raw oil has wide source, and can be used for processing wax oil, wax oil doped residual oil and even normal pressure residual oil. Most importantly, although the reaction and regeneration temperatures of the CPP process are higher than those of the DCC process, the reaction and regeneration temperatures are much lower than those of the conventional steam cracking process, so that the investment and operation cost of the device are much lower.
Nevertheless, the HCC or CPP ethylene production technology using heavy oil as raw material has significant disadvantages: in the current HCC or CPP product distribution, the methane yield is about 11 percent, which wastes valuable petroleum resources.
The current use of methane generally employs a multi-step process involving a very energy intensive syngas process. The direct dehydrogenation of methane or other light alkanes to aromatics requires very high temperatures, for example, dehydrogenation of methane to produce benzene and hydrogen requires a high temperature of 1357 ℃. Therefore, it is difficult to directly utilize methane alone.
The inventor finds out through thermodynamic theoretical calculation on partial reaction that the following reaction can occur according to the following reaction temperature data:
reaction temperature, deg.C, required for chemical reaction equation
1、 1357
2、 607
3、 557
4、 667
5、 787
6、 517
Namely, when ethane, propane, butane and pentane coexist, the aromatization temperature of methane can be reduced by 570-840 ℃, so that the direct conversion of methane can be carried out under a mild condition, the conversion rate of methane can be increased, and the production cost can be greatly reduced.
Disclosure of Invention
The invention aims to provide a process method combining low-carbon alkane aromatization and hydrocarbon oil catalytic thermal cracking processes on the basis of the prior art, so that the low-carbon alkane aromatization process and the hydrocarbon oil catalytic thermal cracking process are complementary in the aspects of heat, raw materials and the like, precious petroleum resources are utilized to the maximum extent, and the product quality and the yield are controlled from the aspect of molecular management according to the difference of reaction mechanisms.
The method provided by the invention comprises the following steps: injecting the preheated heavy petroleum hydrocarbon raw material into a first reactor to contact and react with a hot cracking catalyst from a first regenerator, separating oil gas and a carbon-deposited catalyst after reaction, and feeding the carbon-deposited catalyst into a first regenerator for regeneration; the oil gas after reaction is sent to a subsequent product separation system; injecting the low-carbon alkane into a second reactor, and contacting and reacting the low-carbon alkane with an aromatization catalyst from a second regenerator to convert the low-carbon alkane into aromatic hydrocarbon and hydrogen; separating the obtained reaction product from the carbon-deposited aromatization catalyst, feeding the carbon-deposited aromatization catalyst into a second regenerator for regeneration, and feeding the obtained reaction product into a subsequent product separation system for further separation into products.
The beneficial effects of the invention are mainly reflected in the following aspects:
1. the invention uses two identical or different reactors and regenerators and different catalysts to carry out continuous reaction, and arranges the reaction process according to different production energy of different catalysts and different requirements of the quality and the yield of target products.
2. The raw materials which can be processed by the invention are very flexible and can be arranged to enter different reactors according to the requirements.
3. The catalyst used in the invention has a specific function, and can be used under the environment and condition most suitable for the catalyst, so that the performance of the catalyst can be exerted to the maximum extent, and the best product distribution and product quality are obtained.
4. The different reaction environments arranged in the invention take the difference between different catalysts and reactions into consideration, and are closely related in the aspects of heat utilization, catalyst regeneration, product separation and the like.
5. In industrial implementation of the invention, the single-catalyst two-stage regeneration technology of the existing heavy oil catalytic cracking unit can provide beneficial operation, production and management experiences, thus being easyto be accepted by enterprises.
Detailed Description
In the method of the present invention, the heavy petroleum hydrocarbon feedstock for the first reactor is a conventional catalytic cracking feedstock, such as wax oil, atmospheric residue, vacuum residue, coker wax oil, solvent deasphalted oil, hydrorefined wax oil, residue oil, and the like, and any one or more mixtures thereof may be selected. For the second reactor, the lower alkane refers to a mixture of C1-C5 alkanes, including mixtures of any two or more of methane, ethane, propane, butane, and pentane. The lower alkanes also include isomers of butanes and pentanes, for example, 2-methylpropane, 2-methylbutane, and the like. The low-carbon alkane can be natural gas, can also be a low-carbon alkane mixture rich in methane from an FCC unit, and can also be from other oil refining or chemical engineering units, such as dry gas and liquefied gas of hydrocracking, atmospheric and vacuum 'three-top' low-pressure gas and the like. In the process of the present invention, the lower alkane is preferably a mixture of C1-C5 alkanes from the first reactor, and more preferably a mixture of C1-C5 alkanes rich in methane from the first reactor, for example, the content of methane in the lower alkane may be more than 60 wt%.
The catalyst used in the first reactor of the present invention is preferably catalytic cracking or catalytic thermal cracking catalyst mainly for preparing low carbon olefin, and may be conventional FCC catalyst, which may be one or several kinds selected from Y or HY type zeolite with or without RE, USY, ZSM-5 series zeolite with or without RE, high silicon zeolite with five-membered ring structure, β zeolite, ferrierite and amorphous Si-Al catalyst.
The aromatization catalyst of the invention is an aromatization catalyst aiming at producing aromatic hydrocarbon by directly 'embedding' methane into other low-carbon alkane, particularly propane and butane, the main active component of the catalyst is a porous molecular sieve modified by one or more metals in the 4 th period and the 5 th period of the periodic table of elements containing or not containing Zn, Ga, Mo, Re and the like, and the molecular sieve also contains P in order to improve the activity and the stability of the molecular sieve, and the molecular sieve also contains ZSM-5 series zeolite, β zeolite, HMCM-22 and the like.
The first reactor of the present invention is a conventional catalytic cracking reactor, for example, a riser reactor, a fluidized bed reactor, a down-flow reactor, a millisecond catalytic cracking (MSCC), a Short Contact (SCT), or a fold-over reactor, and modified versions thereof. The second reactor can be any one of a riser reactor, a fluidized bed reactor, a moving bed reactor or a fixed bed reactor.
In the method provided by the invention, the liquid product from the second reactor can be merged with the liquid product from the first reactor to jointly complete the subsequent product separation and recovery processes, and the gas product from the second reactor is preferably returned to the second reactor after being separated from the hydrogen and the low-carbon olefin to continuously participate in the reaction (namely, recycle).
In the method provided by the invention, because the coking rate of the low-carbon alkane in the second reactor is low, in order to maintain the heat balance of the reaction-regeneration system, part or all of the high-temperature flue gas at the outlet of the first regenerator is preferably introduced into the bottom of the second regenerator to provide enough heat for the regeneration of the catalyst in the second regenerator.
The method of the invention can be described in detail as follows: the hot cracking catalyst (650-800 deg.C) from the first regenerator is transferred to the bottom of the first reactor through the first regeneration slide valve, and is lifted by steam, dry gas or other lifting medium, so that the catalyst is fluidized and stably sprayed into the preheated and well atomized heavy petroleum hydrocarbon raw material, and the raw material contacts with the catalyst and is immediately vaporized and reacted. The reaction conditions were as follows: the reaction temperature is 600-800 ℃, preferably 650-750 ℃, the reaction pressure is 0.05-0.40MPa, preferably 0.1-0.25MPa, the weight ratio of the catalyst to the raw material is 1-80: 1, preferably 20-50: 1, the weight ratio of the water vapor to the raw material oil is 0.5-1.5: 1, preferably 0.8-1.2: 1, and the reaction time is 0.05-5.0 seconds, preferably 0.1-3.0 seconds, most preferably 0.5-1.5 seconds. The reaction product, steam and the catalyst (spent catalyst) deposited after the reaction are separated by a quick separation facility (such as a crude cyclone and the like) at the outlet of the first reactor. The spent catalyst enters a first regenerator for burning after being stripped, and the regenerated catalyst returns to the first reactor for recycling. Preferably, a part or all of the high-temperature flue gas discharged from the first regenerator is fed into the second regenerator from the bottom of the second regenerator to provide a certain amount of heat for the regeneration of the aromatization catalyst in the second regenerator.
After the reaction oil gas discharged from the first reactor is fractionated and rectified (gas separation) to separate liquid oil and olefin, the obtained dry gas (mainly methane, ethane), propane and butane fractions or natural gas containing the fractions are injected into the second reactor and contacted with aromatization catalyst from the second regenerator at the temperature of 650-800 ℃, and aromatization reaction is carried out under the conditions that the reaction temperature is 560-780 ℃, preferably 600-750 ℃, the reaction pressure is 0.05-0.40MPa, preferably 0.1-0.25MPa, and the weight ratio of the catalyst to the low-carbon alkane is 1-40: 1, preferably 10-25: 1. The reaction time is 1 to 50 seconds, preferably 5 to 30 seconds. Separating the reacted oil gas and catalyst. The aromatization catalyst after reaction enters a second regenerator for regeneration after steam stripping. And the reaction oil gas enters a product separation unit, wherein the separated liquid product can be combined with the liquid product of the first reactor, and the low-carbon alkane obtained after the hydrogen and the olefin are separated from the gas product returns to the second reactor to continuously participate in the reaction.
The process provided by the present invention is further illustrated below by means of a few specific embodiments, but the invention is not limited thereto.
One embodiment is as follows: two independent reaction-regeneration systems are adopted, and the first reactor and the second reactor are both riser reactors. Under the action of 40-60% atomized steam, the mixture of wax oil preheated to 180-220 deg.C and vacuum residuum (with slag mixing ratio below 40%) contacts with catalytic thermal cracking catalyst from the first regenerator at about 800 deg.C for reaction, and the oil gas and carbon-bearing catalyst flow upward together. The outlet temperature of the first riser is controlled below 780 ℃. After about 0.5-1.0 second, the oil gas and the catalyst enter a secondary cyclone separator for separation, the catalyst enters a stripping section of a first settler connected with a first reactor, enters a first regenerator for regeneration after steam stripping, and high-temperature regeneration flue gas enters a second regenerator from the bottom of the second regenerator. The top pressure of the first settler is 0.20MPa or less. The oil gas enters a separation system, the low-carbon alkane rich in methane and/or the natural gas rich in the low-carbon alkane after the liquid products such as gasoline, diesel oil and the like and the gas olefin are separated enter a second riser reactor, and the low-carbon alkane rich in methane and/or the natural gas rich in the low-carbon alkane and an aromatization catalyst which comes from a second regenerator and has the temperature of about 800 ℃ are subjected to aromatization reaction that the methane is directly embedded into other low-carbon alkanes. The outlet temperature of the second riser is controlled below 780 ℃. After about 10 seconds, the oil gas and the carbon-containing aromatization catalyst enter a secondary cyclone of a second settler connected with the outlet of a second riser, the oil gas enters a fractionation system, and the carbon-containing aromatization catalyst is stripped and then enters a second regenerator for regeneration. The top pressure of the second settler is 0.15MPa or less.
The second embodiment: the first reactor is a riser reactor, and the second reactor is a moving bed reactor. Under the action of 40-80% atomized steam, the mixture of wax oil preheated to 180-220 deg.C and vacuum residuum (slag mixing ratio is below 60%) is contacted with catalytic cracking catalyst from first regenerator and whose temperature is below 800 deg.C, and reacted, and the oil gas and carbon-bearing catalyst can be upwards flowed together. Outlet temperature of the first riserControlled below 780 ℃. After about 0.5-1.0 second, the oil gas and the catalyst enter a secondary cyclone separator for separation, the catalyst enters a stripping section of a first settler and enters a first regenerator for regeneration after steam stripping, and high-temperature regeneration flue gas enters a second regenerator from the bottom of the second regenerator. Top pressure of the first settlerIs 0.20MPa or less. After oil gas is separated, dry gas, propane, butane and natural gas enter a second reactor (moving bed reactor) for less than 30h-1Under the conditions of space velocity below 780 ℃, reaction temperature below 780 ℃ and top pressure of the second settler of 0.15MPa, aromatization reaction of directly embedding methane into low-carbon alkane occurs. After 30 seconds, the oil gas goes to a fractionation system after passing through a secondary cyclone separation catalyst. The catalyst enters a second regenerator for coke burning regeneration after steam stripping. The moving speed of the moving bed is 10 t/h.
The third embodiment: the first reactor is a riser reactor, and the second reactor is a fixed bed reactor. Under the action of 25-60% atomized steam, the mixture of wax oil preheated to 180-220 deg.C and vacuum residuum (slag mixing ratio is below 60%) is contacted with heavy oil catalytic cracking catalyst from first regenerator and whose temperature is below 780 deg.C, and reacted, and the oil gas and carbon-carrying catalyst can be upwards flowed together. The outlet temperature of the first riser is controlled below 760 ℃. After about 0.5-1.5 seconds, the oil gas and the catalyst enter a secondary cyclone separator for separation, the catalyst enters a stripping section of a first settler, the top pressure of the first settler is below 0.20MPa, and the catalyst enters a first regenerator for regeneration after steam stripping. Leading out a part of high-temperature regeneration flue gas, and simultaneously supplementing a proper amount of fuel into the high-temperature regeneration flue gas to reduce the oxygen content of the flue gas to be below 0.001 percent. After oil gas is separated, oxygen-free high-temperature flue gas, dry gas, propane, butane and natural gas enter a second reactor (fixed bed reactor) for less than 30h-1Under the conditions of space velocity of the methane, reaction temperature below 780 ℃ and top pressure of 0.15MPa, the aromatization reaction of directly embedding methane into low-carbon alkane occurs. After 30 seconds the oil and gas go to separate or combined fractionation systems. The gas separated from the separated gas is separated by a separate fractionation system, most of CO2 in the gas is removed, and then the gas is combined with the gas separated from the outlet of the first reactor, and the liquid product is directly reacted with the first reactorThe liquids separated at the outlet of the vessel are combined. One or more fixed bed reactors may be provided. The life of the aromatization catalyst in the fixed bed is generally half a year or more. After the aromatization catalyst is deactivated, switching to another reactor (when more than one reactor is used), or cutting off the feed to make coke-burning regeneration.
The following examples further illustrate the process provided by the present invention, but the invention is not limited thereto. Properties of the feed oil, natural gas and catalyst in the examples are shown in tables 1 to 3. Wherein, the catalyst 1 is a catalytic thermal cracking catalyst, the catalyst is produced by Qilu catalytic Li factory of China petrochemical company, and the trade mark is CIP-1; the catalyst 2 is an aromatization catalyst which is industrially produced by three petroleum plants of the Fushun petrochemical company, and the commodity brand is LAC-1.
Examples
This example illustrates: the method provided by the invention can organically combine the catalytic thermal cracking process and the low-carbon alkane aromatization process, and directly embed low-carbon alkanes such as methane into other low-carbon alkanes under mild conditions, thereby converting the low-carbon alkanes into BTX.
The tests were carried out on a continuous reaction-regeneration medium-riser FCC unit using feed oil 2 as listed in table1 and catalyst 1 as listed in table 2. The test procedure was as follows: the catalyst 1 is first aged on a medium-sized aging apparatus. The aging conditions were 790 ℃ and 100% steam for 27 hours. Raw oil and high-temperature water vapor are mixed and then enter a riser reactor to contact and react with a catalyst 1. The reaction product, steam and spent catalyst are separated in the settler, the reaction product is further separated into gas and liquid products, the spent catalyst enters a regenerator for burning after steam stripping, and the regenerated catalyst is recycled. And separating the mixture of the lower alkanes such as methane, ethane, propane and the like from the obtained gas product. The mixture of the lower alkanes and the natural gas in table 3 are mixed individually or with dry gas in a certain ratio (e.g. 1: 1). In another small fixed bed apparatus, the gaseous hydrocarbon mixture is contacted with the catalyst 2 and reacted. The reaction product was isolated. Tables 4.1, 4.2 show the experimental conditions, the experimental results and the product properties. As can be seen from tables 4.1 and 4.2, the method provided by the present invention can increase the production of a large amount of low-carbon olefins such as ethylene and propylene, and can convert low-carbon alkanes with low equivalent values such as methane and ethane into high-value liquid hydrocarbon compounds, most of which are BTX.
TABLE 1
| Raw material numbering | Starting materials 1 | Raw material 2 | ||
| Density (20 ℃) kg/m3 | 890.6 | 882.6 | ||
| Freezing point, deg.C | 43 | 46 | ||
| Carbon Residue (CCR), wt.% | 4.3 | 2.9 | ||
| Bromine number, gBr/100g | 3.6 | 4.6 | ||
| Kinematic viscosity mm2/s | 80℃ | 44.18 | 34.12 | |
| 100℃ | 24.84 | 19.18 | ||
| Yuan Vegetable extract Group of Become into | Carbon by weight% | 86.54 | 86.35 | |
| Hydrogen, by weight% | 13.03 | 13.28 | ||
| Sulfur, ppm | 3000 | 2300 | ||
| Nitrogen, ppm | 1300 | 1400 | ||
| Distillation of Program for programming Is divided into Analysis of ℃ | Initial boiling point | 282 | 284 | |
| 10％ | 370 | 438 | ||
| 30％ | 482 | 482 | ||
| 50％ | 553 | 540 | ||
| 70％ | - | 55(55％) | ||
| 90％ | - | - | ||
| End point of distillation | - | - | ||
| Hydrocarbons Family of people Group by weight% Become into | Saturated hydrocarbons | 51.2 | 59.8 | |
| Aromatic hydrocarbons | 29.7 | 26.4 | ||
| Glue | 18.3 | 13.2 | ||
| Asphaltenes | 0.8 | 0.6 | ||
| BMCI | 52 | 50 | ||
TABLE 2
| Catalyst numbering | CAT1 | CAT2 | ||
| Chemical group Finished product, weight% | Alumina oxide | 46.5 | - | |
| Rare earth oxide | 0.93 | - | ||
| Apparent density in kg/m3 | 810 | 690 | ||
| Pore volume, ml/g | 0.114 | 0.212 | ||
| Specific surface area, rice2Per gram | 128 | 295.14 | ||
| MillLoss index in weight percent-1 | 2.4 | 2～4nm[1] | 46.5 | |
| Sieving Composition of By weight percent | 0-40um | 16.6 | 4～6nm[1] | 12.78 |
| 40-80um | 42.0 | 6～10nm[1] | 18.90 | |
| ＞80um | 41.4 | 10～21nm[1] | 10.49 | |
| Slightly active, 790 ℃, 100 percent of water vapor, 27h | 62 | 21～36nm[1] | 8.09 | |
| ＞36nm[1] | 3.24 | |||
[1]Pore size distribution of%
TABLE 3
| Composition of natural gas, in% by volume | Natural gas 1 | Natural gas 2 |
| O2 | 0.04 | 0.03 |
| N2 | 1.40 | 1.22 |
| CO2 | 1.40 | 1.30 |
| CH4 | 85.41 | 93.09 |
| C2H6 | 5.22 | 1.84 |
| C3H8 | 4.80 | 1.70 |
| C4H10 | 1.48 | 0.50 |
| C5H12 | 0.25 | 0.32 |
TABLE 4.1
| Raw oil | Raw material 2 | |
| Catalyst and process for preparing same | CAT1 | |
| The water injection amount is weight percent | 1 | |
| Reaction temperature of | 520 | |
| Ratio of agent to oil | 6 | |
| Residence time, s | 2.0 | |
| Pressure, MPa | 0.08 | |
| Product produced by birth Article (A) Is divided by weight Cloth | Dry gas | 4.49 |
| Liquefied gas | 15.70 | |
| Gasoline (gasoline) | 43.77 | |
| Diesel oil | 24.70 | |
| Oil slurry | 5.09 | |
| Coke | 5.25 | |
| Loss of power | 1.00 | |
| Dry gas production of feedstock Percent by weight | Hydrogen gas | 0.15 |
| Hydrogen sulfide | 0.04 | |
| Methane | 1.35 | |
| Ethane (III) | 0.95 | |
| Ethylene | 1.55 | |
| C3Alkane (I) and its preparation method | 0.15 | |
| Propylene (PA) | 0.30 | |
TABLE 4.2
| Raw materials | Dry gas | Dry gas: natural gas 1: 1 of qi | Dry gas: natural gas Gas 2 is 1: 1 | Natural gas 2 |
| Catalyst and process for preparing same | CAT2 | CAT2 | CAT2 | CAT2 |
| Reaction temperature C | 550 | 600 | 650 | 650 |
| Space velocity, h-1 | 1000 | 1000 | 1800 | 2000 |
| Pressure, MPa | Atmospheric pressure | Atmospheric pressure | Atmospheric pressure | Atmospheric pressure |
| Conversion of methane, m% | 26.01 | 30.54 | 37.23 | 38.15 |
| Aromatic hydrocarbon yield, m% | 12.96 | 18.56 | 23.44 | 25.31 |
| Wherein: benzene, m% | 20.5 | 21.0 | 24.8 | 16.4 |
| Toluene, m% | 28.4 | 29.8 | 32.1 | 23.0 |
| C8Aromatic hydrocarbon, m% | 44.1 | 31.2 | 12.6 | 48.9 |
| C9+Aromatic hydrocarbon, m% | 7.0 | 18.0 | 30.5 | 11.7 |
Claims (14)
1. A directional reaction catalytic thermal cracking method for directly converting low-carbon alkane without oxygen is characterized in that preheated heavy petroleum hydrocarbon raw materials are injected into a first reactor to contact and react with a hot cracking catalyst from a first regenerator, oil gas and a carbon-deposited catalyst after reaction are separated, and the carbon-deposited catalyst enters a first regenerator to be regenerated; the oil gas after reaction is sent to a subsequent product separation system; injecting the low-carbon alkane into a second reactor, and contacting and reacting the low-carbon alkane with an aromatization catalyst from a second regenerator to convert the low-carbon alkane into aromatic hydrocarbon and hydrogen; separating the obtained reaction product from the carbon-deposited aromatization catalyst, feeding the carbon-deposited aromatization catalyst into a second regenerator for regeneration, and feeding the obtained reaction product into a subsequent product separation system for further separation into products.
2. The process of claim 1, wherein said heavy petroleum hydrocarbon feedstock is selected from the group consisting of: any one or more than one mixture of wax oil, atmospheric residue oil, vacuum residue oil, coker wax oil, solvent deasphalted oil, hydrorefined wax oil or residue oil.
3. The process of claim 1, wherein said lower alkane is a mixture of C1-C5 alkanes selected from the group consisting of: methane, ethane, propane, butane and pentane and any two or more of their isomers.
4. The process ofclaim 1 or 3, wherein the lower alkane is derived from natural gas, a catalytic cracking unit, an atmospheric and vacuum unit, hydrocracking or other refinery or chemical plant rich in methane.
5. The process of claim 1 wherein the liquid product in the reaction products from the first and second reactors are processed in a common product separation system; the gas product from the first reactor is injected into the second reactor after removing the low-carbon olefin and the hydrogen as part or all of the low-carbon alkane raw material to participate in the reaction; and the gas product from the second reactor is returned to the second reactor to continuously participate in the reaction after low-carbon olefin and hydrogen are removed.
6. The process according to claim 1, characterized in that part or all of the regeneration flue gas discharged from said first regenerator is introduced into the second regenerator via the bottom of the second regenerator.
7. The process of claim 1, wherein the reaction conditions of the petroleum hydrocarbon feedstock in said first reactor are as follows: the reaction temperature is 600 ℃ and 800 ℃, the reaction pressure is 0.05-0.40Mpa, the weight ratio of the catalyst to the raw material is 1-80: 1, the weight ratio of the water vapor to the raw material oil is 0.5-1.5: 1, and the reaction time is 0.05-3.0 seconds.
8. The process of claim 7, wherein the reaction conditions of the petroleum hydrocarbon feedstock in said first reactor are as follows: the reaction temperature is 650 plus 750 ℃, the reaction pressure is 0.1-0.25Mpa, the weight ratio of the catalyst to the raw material is 20-50: 1, the weight ratio of the water vapor to the raw material oil is 0.8-1.2: 1, and the reaction time is 0.5-1.5 seconds.
9. The process according to claim 1, characterized in that the lower alkane is contacted with the aromatization catalyst from the second regenerator at a temperature of 650-: the reaction temperature is 560-780 ℃, the reaction pressure is 0.05-0.40Mpa, the weight ratio of the catalyst to the low-carbon alkane is 1-40: 1, and the reaction time is 1-50 seconds.
10. The process according to claim 9, characterized in that the reaction conditions of the lower alkane in the second reactor are as follows: the reaction temperature is 600-780 ℃, the reaction pressure is 0.1-0.25Mpa, the weight ratio of the catalyst to the low-carbon alkane is 10-25: 1, and the reaction time is 5-30 seconds.
11. The process of claim 1 wherein the reacted coked catalyst in the first reactor is stripped and then fed to a first regenerator for regeneration.
12. The process according to claim 1, characterized in that the post-reaction carbon-deposited aromatization catalyst in the second reactor is stripped and then fed into a second regenerator for regeneration.
13. The process of claim 4 wherein the lower alkane is a mixture of methane-rich C1-C5 alkanes from the first reactor.
14. The process of claim 1 wherein said cracking catalyst is a catalytic cracking or catalytic pyrolysis catalyst for the primary purpose of producing lower olefins.
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| CN105061127A (en) * | 2015-06-03 | 2015-11-18 | 西北大学 | Lower alkane aromatization reaction-regeneration system construction process |
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