CN112225630A - Method for producing unsym-trimethyl benzene from coal-based raw material - Google Patents
Method for producing unsym-trimethyl benzene from coal-based raw material Download PDFInfo
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- CN112225630A CN112225630A CN202010723480.XA CN202010723480A CN112225630A CN 112225630 A CN112225630 A CN 112225630A CN 202010723480 A CN202010723480 A CN 202010723480A CN 112225630 A CN112225630 A CN 112225630A
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- 239000003245 coal Substances 0.000 title claims abstract description 57
- 239000002994 raw material Substances 0.000 title claims abstract description 47
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 30
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 168
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 132
- GWHJZXXIDMPWGX-UHFFFAOYSA-N 1,2,4-trimethylbenzene Chemical compound CC1=CC=C(C)C(C)=C1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 claims abstract description 72
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 48
- 239000002253 acid Substances 0.000 claims abstract description 42
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000004939 coking Methods 0.000 claims abstract description 21
- 230000029936 alkylation Effects 0.000 claims abstract description 20
- 230000008569 process Effects 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001868 water Inorganic materials 0.000 claims abstract description 11
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000012429 reaction media Substances 0.000 claims abstract description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 7
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 7
- 239000002808 molecular sieve Substances 0.000 claims abstract description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 5
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000012752 auxiliary agent Substances 0.000 claims abstract 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 23
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 13
- 239000008096 xylene Substances 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 9
- 239000012535 impurity Substances 0.000 claims description 8
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000011335 coal coke Substances 0.000 claims description 6
- 239000011280 coal tar Substances 0.000 claims description 6
- 239000000446 fuel Substances 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 150000007513 acids Chemical class 0.000 claims description 5
- 239000012159 carrier gas Substances 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910000421 cerium(III) oxide Inorganic materials 0.000 claims description 3
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 239000002671 adjuvant Substances 0.000 claims 1
- 239000003208 petroleum Substances 0.000 abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 11
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 6
- 239000002131 composite material Substances 0.000 description 4
- 239000000571 coke Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000011286 gas tar Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/80—Mixtures of different zeolites
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- B01J2229/10—After treatment, characterised by the effect to be obtained
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- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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Abstract
The invention relates to a method for producing pseudocumene from coal-based raw materials. The method takes cheap coal-based crude benzene and coal-based crude methanol as raw materials, and adopts the technical scheme that the external specific surface area is large>90m2The method is characterized in that the unsym-trimethyl benzene is produced by using an alkylation catalyst and an anti-coking alkylation reaction medium (hydrogen and water or carbon dioxide and water) which mainly comprise weak acid and medium acid (accounting for more than 95% of the total acid number) in a/g manner and through the processes of acid washing, hydrogenation pretreatment, alkylation reaction, rectification and material circulation, and the unsym-trimethyl benzene is produced in a high selectivity (total package). WhereinThe alkylation reaction is carried out in a fixed bed, a fluidized bed or a moving bed reactor, and the used catalyst is two metal oxide auxiliary agent modified sheet MCM-56, nano needle-shaped ZSM-5, sheet MCM-49, nano Beta molecular sieve or a compound thereof. The method provided by the invention can effectively reduce the production cost of the pseudocumene and thoroughly realize the non-petroleum route production of the pseudocumene.
Description
Technical Field
The invention relates to a method for producing pseudocumene by using coal-based raw materials.
Background
As an important aromatic hydrocarbon raw material, the pseudocumene can be used for producing trimellitic anhydride and mesitylene, and has wide application in the solvent industry, and the demand is increasing year by year. Currently, its production is totally dependent on petroleum resources, mainly by the C produced during catalytic reforming and naphtha cracking9～C10And (4) separating aromatic hydrocarbon fractions. The mineral reserves in China are 'more coal and less oil', the shortage of petroleum becomes one of the main bottlenecks of industrial development in China, the continuous and healthy development of national economy requires that China must develop the production technology of petrochemical raw materials by relying on the advantages of resources, and the nation establishes the strategy of 'replacing oil with coal' as the development direction of energy and resources. Meanwhile, as the largest coal coke production area in China, coke gas and coal tar are main by-products of coking, the coke gas can be further separated to extract and recover a large amount of crude benzene, and heavy components in the coal tar are subjected to hydrocracking and lightening to obtain a crude benzene (containing toluene) product. With the rapid development of the coal chemical industry in recent years, the coking benzene production capacity in China reaches more than 400 ten thousand tons per year, the yield is about 300 ten thousand tons per year, the ratio of the total benzene production is increased to nearly 30 percent (the other is petroleum benzene), and the operation rate of most devices is seriously insufficient. Moreover, the coking benzene can only be used in the fields of maleic anhydride, medicines, pesticides, synthetic rubber, dyes, solvents and the like, and the application range of the coking benzene as a chemical raw material is smaller than that of petroleum benzene, so that the price of the coking benzene is always lower than that of the petroleum benzene, and the development of a new way for converting the coking benzene and downstream products thereof draws wide attention at home and abroad.
The technology for preparing methanol by taking coal coke oven gas and coal synthesis gas as raw materials is mature, and with the recent production of a large number of methanol devices in China, the methanol production capacity is seriously excessive, and the price is continuously lowered. Therefore, aiming at the characteristics of domestic coal conversion and coal chemical industry, the invention provides a method for producing the unsym-trimethyl benzene with low price by taking the coal-based crude benzene and the coal-based crude methanol as raw materials (without separation and purification), adopting a novel alkylation catalyst and an anti-coking alkylation reaction medium, and through integrated clean conversion, high selectivity and low cost, the method is more beneficial to the generation of the unsym-trimethyl benzene, and can thoroughly realize the non-petroleum route high-efficiency production of the unsym-trimethyl benzene.
Disclosure of Invention
The invention aims to solve the problem that the prior pseudocumene is completely produced by depending on a petroleum route, and provides a method for producing the pseudocumene with low cost and low selectivity by using a cheap coal-based raw material. The method takes coal-based crude benzene and coal-based crude methanol as raw materials, adopts a novel alkylation catalyst which has large external specific surface area and mainly weak acid and medium strong acid and an anti-coking alkylation reaction medium, and produces the pseudocumene through the processes of acid washing, hydrogenation pretreatment, alkylation reaction, rectification and material circulation.
A process for preparing meta-trimethyl benzene from coal-base raw material includes such steps as acid washing, hydrogenation pretreatment, alkylation reaction, rectifying and material circulation, and features that the raw coal-base benzene and raw coal-base methanol are used as raw materials, and the alkylation catalyst and coking-resistant alkylation reaction medium with large external specific surface area and mainly weak and medium-strong acids are used.
The preferable selection of the invention is that the mass percentage content of the methanol in the coal-based crude methanol raw material is 80.0-93.0 percent, and other impurity components comprise water, dimethyl ether, ethanol, butanol and pentanol; wherein the coal-based crude methanol is at least one of crude methanol prepared from coal coke oven gas and crude methanol prepared from coal synthesis gas.
Preferably, the coal-based crude benzene is at least one of coking crude benzene and coal tar heavy component light crude benzene; the coal-based crude benzene contains 0.5 to 15.0 mass percent of toluene, a small amount of xylene and other impurities (cyclohexane, nitrogen-containing or sulfur-containing substances) besides benzene.
Preferably, the coal-based crude benzene is subjected to acid washing by a sulfuric acid washing method and then is subjected to hydrogenation pretreatment in a fixed bed reactor, and is subjected to alkylation reaction with coal-based methanol; wherein NiO-MoO3 and Co-MoO3 catalysts are adopted in hydrogenation pretreatment.
As a preference of the present invention, the novel alkylation catalyst is selected from: two metal oxide assistant modified sheet MCM-56, nanometer needle ZSM-5, sheet MCM-49 or nanometer Beta molecular sieve, or two compounds thereof; wherein the two metal oxide assistants are selected from La2O3, CaO, Ce2O3, MgO and CuO, and the mass percentage of the total amount of the metal oxide assistants is 0.1-10.0%.
Preferably, the alkylation catalyst has an external specific surface area of greater than 90m2The acid sites on the outer surface account for more than 30.0 percent of the total acid sites, and the weak acids and the medium and strong acids account for more than 95 percent of the total acid sites.
Preferably, the anti-coking alkylation reaction medium is hydrogen and water or carbon dioxide and water.
Preferably, the alkylation reaction product and unreacted benzene enter a rectification system and sequentially pass through an air stripping tower and a benzene + toluene + xylene separation system, the separated light hydrocarbon is used as a device fuel, and the separated xylene is circularly used as a reaction raw material; the heavy component material flowing out of the xylene separation system enters a pseudocumene rectifying tower and is separated to obtain a high-purity pseudocumene product; and the heavy component material flowing out of the pseudocumene rectifying tower is used as the liquid fuel of the device.
As a preferable aspect of the present invention, the alkylation reactor is one of a fixed bed reactor, a fluidized bed reactor and a moving bed reactor.
Preferably, the alkylation reaction conditions are as follows: the alkylation reaction conditions are as follows: the molar ratio of the coal-based crude methanol to the coal-based crude benzene is 1: 1-1: 6, the reaction pressure is 0.1 MPa-5.0 MPa, the reaction temperature is 350-700 ℃, the molar ratio of an anti-coking alkylation reaction medium to the raw materials is 1: 2-10: 1, and the total mass space velocity is 0.2-10.0 h < -1 >; the molar ratio of the carrier gas to the raw material is 1: 2-10: 1.
In conclusion, the invention has the following beneficial effects:
the total package inlet materials of the process system are cheap coal-based crude benzene and coal-based crude methanol, so that a high-purity pseudocumene product is produced, only a small amount of light hydrocarbon and a small amount of heavy aromatic hydrocarbon are produced as byproducts, and the total package reaction result shows high target product selectivity; and the raw material separation and purification process is omitted, the alkylation catalyst does not need to be frequently replaced or regenerated and circulated, and the pseudocumene is really produced by a non-petroleum route with high selectivity and low cost.
Drawings
FIG. 1 is a process flow diagram of the method for producing pseudocumene from coal-based raw materials according to the present invention.
Detailed description of the invention
The invention is further illustrated by, but not limited to, the following specific examples.
Example 1:
FIG. 1 is a process flow diagram of the method for producing pseudocumene from coal-based raw materials according to the present invention. The method for producing the unsym-trimethyl benzene by using the coal-based raw material comprises the steps of using crude methanol (80.0 percent) prepared from coal synthesis gas, coking crude benzene (containing 90.4 percent by weight of benzene, 8.0 percent by weight of toluene, 1.5 percent by weight of dimethylbenzene and 0.1 percent by weight of other impurities) as raw materials, wherein the coking crude benzene is subjected to sulfuric acid washing and hydrogenation pretreatment (NiO-MoO)3And Co-MoO3Catalyst, fixed bed), and then enters an alkylation reactor (fluidized bed) with crude methanol for catalytic reaction to obtain products mainly comprising pseudocumene, toluene, mixed xylene, a small amount of heavy component aromatic hydrocarbon and light hydrocarbon. The benzene and unreacted benzene enter a rectification system and sequentially pass through a stripping tower and a benzene + toluene + xylene (BTX) separation system, separated light hydrocarbon is used as device fuel, and separated BTX is recycled as reaction raw material; the heavy component material flowing out of the BTX separation system enters a pseudocumene rectifying tower, and a high-purity pseudocumene product is obtained through separation; and the heavy component material flowing out of the pseudocumene rectifying tower is used as the liquid fuel of the device. The catalyst used in the alkylation reaction was 2.0% La2O3And 1.8% Ce2O3The composite modified nanometer needle-shaped ZSM-5 molecular sieve has the external specific surface area of 96m2The number of outer surface acid sites is 34% of the total number of acid sites, and the number of weak acid sites and medium acid sites is 96.8% of the total number of acid sites. The alkylation reaction conditions are as follows: the molar ratio of methanol to aromatic hydrocarbon (BTX) is 1:6, the reaction pressure is normal pressure, the reaction temperature is 350 ℃, the molar ratio of water to the raw material is 1:2, and the total mass space velocity is 4.0h-1(ii) a By using CO2The molar ratio of the carrier gas to the raw material is 3: 1. The method takes cheap coal synthesis gas crude methanol and coking crude benzene as raw materials to realize the production of the pseudocumene with high selectivity and low cost. The reaction data of the whole process system package is as follows: complete conversion of benzene and methanol to aromatic productsThe selectivity of the pseudocumene reaches 94.0 percent. The alkylation catalyst operated for 820h per pass (catalyst deactivation is considered when the methanol conversion in the alkylation reactor is not complete, the same is done in the examples below). Wherein, the method for calculating the selectivity of the pseudocumene in the aromatic hydrocarbon product is as follows (the same as the following examples):
example 2:
based on embodiment 1, the difference from embodiment 1 is that:
the coal-based methanol raw material adopts crude methanol (the methanol content is 93.0 wt%) prepared from coal coke oven gas. The coal-based benzene is a mixture of coking crude benzene and coal tar heavy component light crude benzene, and contains 79.8 wt% of benzene, 15.0 wt% of toluene, 5.0 wt% of xylene and 0.2 wt% of other impurities. The alkylation reactor adopts a fixed bed reactor. The catalyst used in the alkylation reaction is a sheet MCM-56/nano Beta composite molecular sieve compositely modified by 0.04 percent of CuO and 0.1 percent of CaO, and the external specific surface area is 93m2The acid sites on the outer surface account for 32% of the total acid sites, and the weak and medium acid sites account for 98.1% of the total acid sites. The alkylation reaction conditions are as follows: the molar ratio of methanol to aromatic hydrocarbon (BTX) is 1:1, the reaction pressure is 2.0MPa, the reaction temperature is 480 ℃, the molar ratio of water to the raw material is 4:1, and the total mass space velocity is 10.0h-1(ii) a By means of H2The molar ratio of the carrier gas to the raw material is 10: 1. The other process arrangements and raw material selection were the same as in example 1. The reaction data of the whole process system package in this embodiment are as follows: the benzene and the methanol are completely converted, and the selectivity of the pseudocumene in the aromatic hydrocarbon product reaches 95.4 percent. The single pass service life of the alkylation catalyst reaches 2500 h.
Example 3:
based on embodiment 1, the difference from embodiment 1 is that:
the coal-based benzene raw material adopts coked crude benzene and contains 99.19 wt% of benzene, 0.6 wt% of toluene, 0.2 wt% of xylene and 0.01 wt% of other impurities; the coal-based methanol is prepared by mixing crude toluene prepared from coal synthesis gas and crude methanol prepared from coal coke oven gasCompound containing 84.1 wt% methanol; the alkylation reactor adopts a moving bed reactor. The catalyst used in the alkylation reaction is a nano needle-shaped ZSM-5/sheet MCM-49 composite molecular sieve which is compositely modified by 5.0 percent of CdO and 5.0 percent of MgO, and the external specific surface area is 99m2The number of outer surface acid sites accounts for 36% of the total number of acid sites, and the number of weak acid sites and medium acid sites accounts for 97.1% of the total number of acid sites. The alkylation reaction conditions are as follows: the molar ratio of methanol to aromatic hydrocarbon (BTX) is 1:2, the reaction pressure is 5.0MPa, the reaction temperature is 700 ℃, the molar ratio of water to the raw material is 10:1, and the total mass space velocity is 0.2h-1(ii) a By using CO2The molar ratio of the carrier gas to the raw material is 1: 2. Other raw material selection and process arrangement were the same as in example 1. The reaction data of the whole process system package are as follows: the benzene and the methanol are completely converted, and the selectivity of the pseudocumene in the aromatic hydrocarbon product reaches 96.6 percent. The alkylation catalyst has a single-pass life of 1600 h.
Example 4:
based on embodiment 1, the difference from embodiment 1 is that:
the coal-based methanol raw material adopts a mixture of crude methanol prepared from coal synthesis gas and crude methanol prepared from coke oven gas (the methanol content is 86.3 wt%); coal-based benzene is coal tar heavy component light crude benzene (containing 79.0 wt% of benzene, 15.0 wt% of toluene, 5.0 wt% of xylene and 1.0 wt% of other impurities); the catalyst used in the alkylation reaction is a flaky MCM-49/nano Beta composite molecular sieve modified by 3.0 percent of CuO and 1.0 percent of MgO, and the external specific surface area is 92m2The acid sites on the outer surface account for 35% of the total acid sites, and the weak and medium acid sites account for 95.7% of the total acid sites. Other raw material selection, process arrangement and reaction conditions were the same as in example 2. The reaction data of the whole process system package is as follows: the benzene and the methanol are completely converted, and the selectivity of the pseudocumene in the aromatic hydrocarbon product reaches 96.3 percent. The alkylation catalyst has a single-pass life of 2700 h.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention and do not limit the spirit and scope of the present invention. Various modifications and improvements of the technical solutions of the present invention may be made by those skilled in the art without departing from the design concept of the present invention, and the technical contents of the present invention are all described in the claims.
Claims (10)
1. The method for producing the pseudocumene from the coal-based raw materials is characterized in that the pseudocumene is produced by taking the coal-based crude benzene and the coal-based crude methanol as the raw materials, adopting an alkylation catalyst and a coking-resistant alkylation reaction medium which have large external specific surface area and mainly weak acid and medium strong acid, and carrying out the processes of acid washing, hydrogenation pretreatment, alkylation reaction, rectification and material circulation.
2. The method for producing pseudocumene according to claim 1, wherein the mass percent of methanol in the coal-based crude methanol raw material is 80.0-93.0%, and other impurity components comprise water, dimethyl ether, ethanol, butanol and pentanol; wherein the coal-based crude methanol is at least one of crude methanol prepared from coal coke oven gas and crude methanol prepared from coal synthesis gas.
3. The method for producing pseudocumene from the coal-based raw material according to claim 1 or 2, characterized in that the coal-based crude benzene is at least one of coking crude benzene and coal tar heavy component light crude benzene; the coal-based crude benzene contains 0.5 to 15.0 mass percent of toluene, a small amount of xylene and other impurities (cyclohexane, nitrogen-containing or sulfur-containing substances) besides benzene.
4. The method for producing unsym-trimethyl benzene from coal-based raw material as claimed in claim 3, wherein the coal-based crude benzene is subjected to hydrogenation pretreatment in a fixed bed reactor after being subjected to acid washing by sulfuric acid washing, and is subjected to alkylation reaction with coal-based methanol; wherein NiO-MoO is adopted in hydrogenation pretreatment3And Co-MoO3A catalyst.
5. The process for the production of pseudocumene according to claim 1 wherein the novel alkylation catalyst is selected from the group consisting of: flake MCM-56, nano needle-shaped ZSM-5 and flake modified by two metal oxide additivesMCM-49 or Beta molecular sieve, or their two compounds; wherein the two metal oxide adjuvants are selected from La2O3、CaO、Ce2O3MgO and CuO, and the mass percentage of the total amount of the metal oxide auxiliary agent is 0.1-10.0%.
6. The method for producing pseudocumene according to claim 1, wherein the external specific surface area of the alkylation catalyst is greater than 90m2The acid sites on the outer surface account for more than 30.0 percent of the total acid sites, and the weak acids and the medium and strong acids account for more than 95 percent of the total acid sites.
7. The method for producing pseudocumene according to claim 1 wherein the anti-coking alkylation reaction medium is hydrogen and water or carbon dioxide and water.
8. The method for producing unsym-trimethyl benzene from coal-based raw material as claimed in claim 1, wherein the alkylation reaction product and unreacted benzene enter a rectification system, and sequentially pass through an air stripping tower and a benzene + toluene + xylene separation system, the separated light hydrocarbon is used as fuel of a device, and the separated xylene is recycled as reaction raw material; the heavy component material flowing out of the xylene separation system enters a pseudocumene rectifying tower and is separated to obtain a high-purity pseudocumene product; and the heavy component material flowing out of the pseudocumene rectifying tower is used as the liquid fuel of the device.
9. The method of claim 1, wherein the alkylation reactor is one of a fixed bed reactor, a fluidized bed reactor and a moving bed reactor.
10. The method for producing pseudocumene from coal-based raw material according to claim 1, wherein the alkylation reaction conditions are as follows: the molar ratio of the coal-based crude methanol to the coal-based crude benzene is 1: 1-1: 6, the reaction pressure is 0.1 MPa-5.0 MPa, the reaction temperature is 350-700 ℃, and the coking-resistant alkylation reaction mediumThe molar ratio of the raw material to the raw material is 1: 2-10: 1, and the total mass airspeed is 0.2-10.0 h-1(ii) a The molar ratio of the carrier gas to the raw material is 1: 2-10: 1.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1210786A (en) * | 1968-04-18 | 1970-10-28 | Mobil Oil Corp | Hydrocarbon conversion employing highly selective catalysts |
| CN101654394A (en) * | 2009-09-11 | 2010-02-24 | 上海卓悦化工科技有限公司 | Method for synthesizing BTX aromatic methyl into unsym-trimethyl benzene |
| CN107473918A (en) * | 2017-07-14 | 2017-12-15 | 同济大学 | The method of coal-based feedstocks production paraxylene, ortho-xylene and pseudocumene |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1210786A (en) * | 1968-04-18 | 1970-10-28 | Mobil Oil Corp | Hydrocarbon conversion employing highly selective catalysts |
| CN101654394A (en) * | 2009-09-11 | 2010-02-24 | 上海卓悦化工科技有限公司 | Method for synthesizing BTX aromatic methyl into unsym-trimethyl benzene |
| CN107473918A (en) * | 2017-07-14 | 2017-12-15 | 同济大学 | The method of coal-based feedstocks production paraxylene, ortho-xylene and pseudocumene |
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