CN115572213A - Process for coproduction of 1, 4-butanediol and liquid ammonia by coal gasification coupled with coal coking - Google Patents

Process for coproduction of 1, 4-butanediol and liquid ammonia by coal gasification coupled with coal coking Download PDF

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CN115572213A
CN115572213A CN202211389981.4A CN202211389981A CN115572213A CN 115572213 A CN115572213 A CN 115572213A CN 202211389981 A CN202211389981 A CN 202211389981A CN 115572213 A CN115572213 A CN 115572213A
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gas
butanediol
liquid ammonia
coke oven
hydrogen
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张建国
周云辉
李龙
靳鹏
李飞
谷小虎
王育红
席波
张俊树
李英英
张华�
李春涛
胡延韶
朱亚楠
王少华
张静
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China Pingmei Shenma Holding Group Co ltd
Pingdingshan Tianan Coal Mining Co Ltd
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China Pingmei Shenma Holding Group Co ltd
Pingdingshan Tianan Coal Mining Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • C07C29/172—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with the obtention of a fully saturated alcohol
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/047—Pressure swing adsorption
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/04—Preparation of ammonia by synthesis in the gas phase
    • C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
    • C01C1/0488—Processes integrated with preparations of other compounds, e.g. methanol, urea or with processes for power generation
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/0425—Catalysts; their physical properties
    • C07C1/043—Catalysts; their physical properties characterised by the composition
    • C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
    • C07C2/82—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
    • C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
    • C07C29/42—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing triple carbon-to-carbon bonds, e.g. with metal-alkynes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/72—Other features
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
    • C10K3/04—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment reducing the carbon monoxide content, e.g. water-gas shift [WGS]
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with rare earths or actinides

Abstract

The invention provides a process for coproducing 1, 4-butanediol and liquid ammonia by coal gasification coupled coal coking, which comprises a raw coke oven gas purification process, a coal gasification process, a pressure swing adsorption hydrogen extraction process, a raw coke oven gas conversion process, a decarburization process, a methanation process, a cryogenic process, an oxidation acetylene preparation process, an alkynaldehyde method BDO process, a tail gas liquid ammonia preparation process and the like, so that the coproduction of 1, 4-butanediol, liquefied natural gas, acetylene and liquid ammonia is realized, the intensification of production equipment can be realized, the production efficiency can be improved, the problems of serious process pollution, high energy consumption and the like caused by adopting calcium carbide as a production raw material of 1, 4-butanediol in the prior art can be avoided while reasonably utilizing raw coke oven gas (raw coke oven gas), and primary hydrogen, secondary hydrogen and nitrogen in the tail gas can be utilized to produce liquid ammonia, so that the utilization rate of the production raw materials is further improved, and the aim of reducing the production cost is fulfilled.

Description

Process for coproduction of 1, 4-butanediol and liquid ammonia by coal gasification coupled with coal coking
Technical Field
The invention relates to the technical field related to BDO production, in particular to a process for coproducing 1, 4-butanediol and liquid ammonia by coal gasification coupled with coal coking.
Background
1, 4-butanediol BDO for short is an organic matter, has a molecular formula of C4H10O2 and a molecular weight of 90.12, is colorless or light yellow oily liquid in appearance, is combustible, has a freezing point of 20.1 ℃ and a refractive index of 1.4461, can be dissolved in methanol, ethanol and acetone, is slightly soluble in ether, has hygroscopicity and bitter smell, and has slight sweet taste when entering the mouth; it can be used as solvent and moisturizer, and can also be used for preparing plasticizer, medicine, polyester resin, polyurethane resin, etc.;
in the existing BDO production process by the alkynal method, acetylene is generally obtained by a traditional calcium carbide hydrolysis method or a natural gas partial oxidation method, the calcium carbide production process is seriously polluted and high in energy consumption, natural gas resources are seriously in shortage at the present stage, and abundant coke oven gas faces the technical current situation of efficient utilization;
however, in the prior art, coke oven gas is often used as fuel, which not only causes huge waste, but also causes pollution and waste, so that the comprehensive utilization of coke oven gas becomes the key for the survival and development of coking enterprises.
Disclosure of Invention
The invention aims to provide a process for coproducing 1, 4-butanediol and liquid ammonia by coal gasification coupled with coal coking, so as to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: a coal gasification coupling coal coking coproduction process for preparing 1, 4-butanediol and liquid ammonia comprises the following steps:
the method comprises the following steps: the method comprises the following steps of (1) raw gas purification, wherein in the raw gas purification, raw gas is subjected to dust removal purification through dust removal equipment to obtain pretreated raw gas;
step two: a coal gasification process, wherein in the coal gasification process, coal powder is dried at the temperature of 100 ℃, then the coal powder is added into a gasification furnace, and a synthesis gas reaction is carried out at the pressure of 4-7 KPa and the temperature of 1000 ℃ to generate primary carbon monoxide gas and primary hydrogen gas;
step three: in the pressure swing adsorption hydrogen extraction process, primary carbon monoxide gas is liquefied through temperature reduction treatment, and then primary hydrogen gas is separated;
step four: the raw coke oven gas conversion process comprises the steps of conveying pretreated raw coke oven gas into a reaction tower, performing CO conversion reaction on the obtained coke oven gas and water vapor by using a conversion catalyst under the conditions of 190-480 ℃ and 3-5MPa, and then converting CO and primary carbon monoxide gas in the coke oven gas into secondary hydrogen and generating secondary coke oven gas;
step five: a decarburization process, wherein in the decarburization process, the secondary coke oven gas is subjected to decarburization reaction through a decarburization solvent to obtain a tertiary coke oven gas;
step six: performing a methanation process, wherein in the methanation process, the three times of coke oven gas are subjected to catalytic reaction under the action of a methanation catalyst to obtain CO and CO in the three times of coke oven gas 2 Converting into methane;
step seven: a cryogenic process, wherein in the cryogenic process, after the mixed gas of methane obtained in the methanation process and tertiary coke oven gas is dried and dehydrated, a mixed refrigerant is adopted for liquefaction at a temperature of between-165 and-162 ℃ to produce liquid natural gas with the methane content of more than 98wt%, and secondary hydrogen and nitrogen as byproducts are generated at the same time;
step eight: in the process of preparing acetylene by using an oxidation method, liquid natural gas obtained by cryogenic technological process treatment is preheated to 650-750 ℃, then is mixed in a mixer of an acetylene cracking furnace, and methane is partially oxidized and cracked at the temperature of 1300-1500 ℃ to obtain cracked gas containing acetylene;
step nine: in the process of preparing BDO by adopting an alkynal method, primary acetylene gas is separated from pyrolysis gas, the primary acetylene gas is purified to obtain secondary acetylene gas, the secondary acetylene gas and formaldehyde are used as raw materials, 1, 4-butynediol is generated under the action of a catalyst, and the 1, 4-butynediol is added into a hydrogen reactor and is hydrogenated with hydrogen to generate a crude 1, 4-butanediol product;
step ten: the technical process of preparing the liquid ammonia from the tail gas comprises the steps of adding primary hydrogen in a pressure swing adsorption hydrogen extraction process and secondary hydrogen and nitrogen in a cryogenic technological process into a synthesis tower, adding an ammonia preparation catalyst to react to generate ammonia gas, and cooling to form the liquid ammonia.
Preferably, the shift catalyst used in the raw coke oven gas shift process is a basf K8-11 sulfur-tolerant shift catalyst, and the mass ratio of the water vapor to the coke oven gas is as follows: 0.4-0.5.
Preferably, the decarbonization solvent comprises 80wt% to 91wt% of the main agent, 5wt% to 16 wt% of the activating agent and 0.75wt% to 4wt% of the auxiliary agent.
Preferably, the main agent comprises methyldiethanolamine and triethanolamine or methyldiethanolamine and diisopropylethanolamine, the activating agent is a mixture of primary amine and secondary amine, and the primary amine is hydroxyethyl ethylenediamine or 2-amino-2-methyl-1, 3-propanediol; the secondary amine is diethanolamine or methyl monoethanolamine, and the auxiliary agent comprises hydroxyethyl hexahydro-s-triazine and sodium sulfite.
Preferably, the catalyst in the methanation process is a nickel-based catalyst, and the catalyst substrate is Al 2 O 3 The catalyst promoter is La or Ce, and the catalyst contains 20-30 wt% of nickel oxide, 4-6 wt% of catalyst promoter and 64-76 wt% of Al 2 O 3 。
Preferably, in the process of preparing BDO by the alkynal method, in the process of separating acetylene gas from cracking gas, the reaction temperature is 50-75 ℃, and the pressure is 1.5-2.5 MPa, and in the process of catalyzing secondary acetylene gas and formaldehyde to generate 1, 4-butynediol, the reaction temperature is 120-150 ℃, and the pressure is 15-25 MPa.
Preferably, the low-boiling-point impurities and most of water in the crude 1, 4-butanediol product obtained in the BDO preparation by the alkyne-aldehyde method are firstly separated to obtain a 1, 4-butanediol solution with the concentration of 95 wt%; then removing a part of high-boiling-point residues from the 95wt% 1, 4-butanediol solution, recovering to obtain a high-purity 1, 4-butanediol solution, and further purifying to obtain a 1, 4-butanediol finished product with the final concentration of more than 99.5 wt%.
Preferably, in the process of preparing liquid ammonia from tail gas, primary hydrogen, secondary hydrogen and nitrogen are added into the synthesis tower for reaction, and the catalysts used in the reaction process are FeO and Fe 2 O 3 And FeO and Fe 2 O 3 The mass ratio of (2) is 9.
Preferably, in the process of preparing liquid ammonia from tail gas, after multi-stage compression is performed inside the synthesis tower, the internal pressure of the synthesis tower reaches 32MPa, and the temperature in the synthesis tower is controlled within the range of 450-500 ℃.
Preferably, in the process of preparing liquid ammonia from tail gas, most of water and hydrogen sulfide in the crude ammonia gas are removed through three-stage segregation, and the conditions of the three-stage segregation are as follows: the first-stage segregation temperature is 120-200 ℃, and the pressure after segregation is 0.6-2.0 MPa; the secondary segregation temperature is 90-150 ℃, and the pressure after segregation is 0.55-1.5 MPa; the tertiary segregation temperature is 30-70 ℃, the pressure after segregation is 0.5-1.0 MPa, the ammonia gas after segregation is cooled to-30-20 ℃, and the ammonia gas is converted into liquid ammonia.
Compared with the prior art, the invention has the beneficial effects that: the invention comprises the following steps: the process comprises the steps of raw coke oven gas purification, coal gasification, pressure swing adsorption hydrogen extraction, raw coke oven gas conversion, decarburization, methanation, copious cooling, acetylene preparation by oxidation, BDO preparation by alkynaldehyde and liquid ammonia preparation by tail gas, and the like, so that the co-production of 1, 4-butanediol, liquefied natural gas, acetylene and liquid ammonia is realized, the intensification of production equipment can be realized, the production efficiency can be improved, the problems of serious process pollution, high energy consumption and the like caused by the fact that calcium carbide is used as a production raw material of 1, 4-butanediol in the prior art can be avoided while raw coke oven gas (raw coke oven gas) is reasonably utilized, primary hydrogen, secondary hydrogen and nitrogen in the tail gas can be utilized to produce liquid ammonia, the utilization rate of the production raw materials can be further improved, and the aim of reducing the production cost can be realized.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example one
The invention provides a technical scheme that: a process for coproducing 1, 4-butanediol and liquid ammonia by coal gasification coupled with coal coking comprises the following steps:
the method comprises the following steps: the method comprises the following steps of (1) carrying out a raw gas purification process, wherein in the raw gas purification process, raw gas is firstly subjected to dust removal purification through dust removal equipment to obtain pretreated raw gas;
step two: a coal gasification process, wherein in the coal gasification process, coal powder is dried at the temperature of 100 ℃, then the coal powder is added into a gasification furnace, and a synthesis gas reaction is carried out at the pressure of 6KPa and the temperature of 1000 ℃ to generate primary carbon monoxide gas and primary hydrogen gas;
step three: in the pressure swing adsorption hydrogen extraction process, primary carbon monoxide gas is liquefied through temperature reduction treatment, and then primary hydrogen gas is separated;
step four: the raw gas conversion process comprises the following steps of conveying pretreated raw gas into a reaction tower, performing CO conversion reaction on the obtained coke oven gas and water vapor by using a conversion catalyst under the pressure conditions of 400 ℃ and 4MPa, converting CO in the coke oven gas and primary carbon monoxide gas to generate secondary hydrogen and generate secondary coke oven gas, wherein the conversion catalyst used in the raw gas conversion process is a sulfur-tolerant conversion catalyst of Basv K8-11, and the mass ratio of the water vapor to the coke oven gas is as follows: 0.5;
step five: the method comprises the following steps of (1) performing decarburization reaction on secondary coke oven gas by using a decarburization solvent in the decarburization process to obtain tertiary coke oven gas, wherein the decarburization solvent comprises 80wt% of a main agent, 16 wt% of an activating agent and 4wt% of an auxiliary agent, the main agent comprises methyldiethanolamine and triethanolamine or methyldiethanolamine and diisopropylethanolamine, the activating agent is a mixture of primary amine and secondary amine, and the primary amine is hydroxyethyl ethylenediamine or 2-amino-2-methyl-1, 3-propanediol; the secondary amine is diethanolamine or methyl monoethanolamine, and the auxiliary agent comprises hydroxyethyl hexahydro-s-triazine and sodium sulfite;
step six: the methanation process is that the three coke oven gases are subjected to catalytic reaction under the action of a methanation catalyst to react CO and CO in the three coke oven gases 2 The catalyst is nickel-based catalyst in the methanation process, and the catalyst substrate is Al 2 O 3 The catalyst promoter is La or Ce, and the catalyst contains 25wt% of nickel oxide, 5wt% of catalyst promoter and 70wt% of Al 2 O 3 ；
Step seven: a cryogenic process, wherein in the cryogenic process, after the mixed gas of methane obtained in the methanation process and tertiary coke oven gas is dried and dehydrated, the mixed gas is liquefied at minus 164 ℃ by using mixed refrigerant to produce liquid natural gas with the methane content of more than 98wt%, and secondary hydrogen and nitrogen as byproducts are generated at the same time;
step eight: in the process of preparing acetylene by an oxidation method, liquid natural gas obtained by cryogenic process treatment is preheated to 720 ℃, then mixed in a mixer of an acetylene cracking furnace, and methane is partially oxidized and cracked at 1450 ℃ to obtain cracked gas containing acetylene;
step nine: in the BDO (acetylenic aldehyde method), separating primary acetylene gas from pyrolysis gas, purifying the primary acetylene gas to obtain secondary acetylene gas, using the secondary acetylene gas and formaldehyde as raw materials, generating 1, 4-butynediol under the action of a catalyst, adding the 1, 4-butynediol into a hydrogen reactor, and hydrogenating with hydrogen to generate a crude 1, 4-butanediol product, wherein in the BDO (acetylenic aldehyde method), in the BDO process, the reaction temperature is 70 ℃, the pressure is 2.2MPa, in the process of generating the 1, 4-butynediol by catalyzing the secondary acetylene gas and the formaldehyde, the reaction temperature is 135 ℃ and the pressure is 23MPa, and in the BDO process, the crude 1, 4-butanediol product obtained in the BDO process is separated, low-boiling-point impurities and most of water are firstly separated to obtain a 1, 4-butanediol solution with the concentration of 95 wt%; then removing a part of high-boiling-point residues from the 95wt% 1, 4-butanediol solution, recovering to obtain a high-purity 1, 4-butanediol solution, and further purifying to obtain a 1, 4-butanediol finished product with the final concentration of more than 99.5 wt%;
step ten: in the technical process of preparing liquid ammonia from tail gas, primary hydrogen in the process of extracting hydrogen by pressure swing adsorption and secondary hydrogen and nitrogen in the process of copious cooling are added into a synthesis tower, an ammonia preparation catalyst is added to react to generate ammonia gas, liquid ammonia is formed by cooling treatment, primary hydrogen, secondary hydrogen and nitrogen are added into the synthesis tower to react in the technical process of preparing liquid ammonia from tail gas, and the catalyst used in the reaction process is FeO and Fe 2 O 3 And FeO and Fe 2 O 3 The mass ratio of (3) is 9, in the technical process of preparing liquid ammonia from tail gas, after multi-stage compression is carried out in the synthesis tower, the internal pressure of the synthesis tower is up to 32MPa, the temperature in the synthesis tower is controlled to be within the range of 480 ℃, in the technical process of preparing liquid ammonia from tail gas, most of water and hydrogen sulfide in crude ammonia are removed through three-stage segregation, and the conditions of the three-stage segregation are as follows: the primary segregation temperature is 170 ℃, and the pressure after segregation is 1.7MPa; the secondary segregation temperature is 130 ℃, and the pressure after segregation is 1.2MPa; the tertiary segregation temperature is 56 ℃, the pressure after segregation is 0.8MPa, the ammonia gas after segregation is cooled to-20 ℃, and the ammonia gas is converted into liquid ammonia.
Example two
The invention provides a technical scheme that: a process for coproducing 1, 4-butanediol and liquid ammonia by coal gasification coupled with coal coking comprises the following steps:
the method comprises the following steps: the method comprises the following steps of (1) carrying out a raw gas purification process, wherein in the raw gas purification process, raw gas is firstly subjected to dust removal purification through dust removal equipment to obtain pretreated raw gas;
step two: a coal gasification process, wherein in the coal gasification process, coal powder is dried at 100 ℃ and then added into a gasification furnace, and synthesis gas reaction is carried out at the pressure of 6KPa and the temperature of 1000 ℃ to generate primary carbon monoxide gas and primary hydrogen gas;
step three: in the pressure swing adsorption hydrogen extraction process, primary carbon monoxide gas is liquefied through temperature reduction treatment, and then primary hydrogen gas is separated;
step four: the raw coke oven gas conversion process comprises the following steps of conveying pretreated raw coke gas into a reaction tower, carrying out CO conversion reaction on the obtained coke oven gas and water vapor by using a conversion catalyst under the pressure conditions of 400 ℃ and 4MPa, converting CO in the coke oven gas and primary carbon monoxide gas to generate secondary hydrogen and generate secondary coke oven gas, wherein the conversion catalyst used in the raw coke gas conversion process is a Basff K8-11 sulfur-resistant conversion catalyst, and the mass ratio of the water vapor to the coke oven gas is as follows: 0.5;
step five: the method comprises the following steps of (1) performing decarburization reaction on secondary coke oven gas by using a decarburization solvent in the decarburization process to obtain tertiary coke oven gas, wherein the decarburization solvent comprises 83wt% of a main agent, 14 wt% of an activating agent and 3wt% of an auxiliary agent, the main agent comprises methyldiethanolamine and triethanolamine or methyldiethanolamine and diisopropylethanolamine, the activating agent is a mixture of primary amine and secondary amine, and the primary amine is hydroxyethyl ethylenediamine or 2-amino-2-methyl-1, 3-propanediol; the secondary amine is diethanolamine or methyl monoethanolamine, and the auxiliary agent comprises hydroxyethyl hexahydro-s-triazine and sodium sulfite;
step six: the methanation process is that the three coke oven gases are subjected to catalytic reaction under the action of a methanation catalyst to react CO and CO in the three coke oven gases 2 The catalyst is nickel-based catalyst in the methanation process, and the catalyst substrate is Al 2 O 3 The catalyst promoter is La or Ce, and the catalyst contains 25wt% of nickel oxide, 5wt% of catalyst promoter and 70wt% of Al 2 O 3 ；
Step seven: a cryogenic process, wherein in the cryogenic process, after the mixed gas of methane obtained in the methanation process and the tertiary coke oven gas is dried and dehydrated, the mixed gas is liquefied at a temperature of minus 164 ℃ by using a mixed refrigerant, so as to produce liquid natural gas with the methane content of more than 98wt%, and meanwhile, secondary hydrogen and nitrogen which are byproducts are generated;
step eight: in the process of preparing acetylene by an oxidation method, liquid natural gas obtained by cryogenic process treatment is preheated to 720 ℃, then mixed in a mixer of an acetylene cracking furnace, and methane is partially oxidized and cracked at 1450 ℃ to obtain cracked gas containing acetylene;
step nine: in the BDO (acetylenic aldehyde method), separating primary acetylene gas from pyrolysis gas, purifying the primary acetylene gas to obtain secondary acetylene gas, using the secondary acetylene gas and formaldehyde as raw materials, generating 1, 4-butynediol under the action of a catalyst, adding the 1, 4-butynediol into a hydrogen reactor, and hydrogenating with hydrogen to generate a crude 1, 4-butanediol product, wherein in the BDO (acetylenic aldehyde method), in the BDO process, the reaction temperature is 70 ℃, the pressure is 2.2MPa, in the process of generating the 1, 4-butynediol by catalyzing the secondary acetylene gas and the formaldehyde, the reaction temperature is 135 ℃ and the pressure is 23MPa, and in the BDO process, the crude 1, 4-butanediol product obtained in the BDO process is separated, low-boiling-point impurities and most of water are firstly separated to obtain a 1, 4-butanediol solution with the concentration of 95 wt%; then removing a part of high-boiling-point residues from the 95wt% 1, 4-butanediol solution, recovering to obtain a high-purity 1, 4-butanediol solution, and further purifying to obtain a 1, 4-butanediol finished product with the final concentration of more than 99.5 wt%;
step ten: in the technical process of preparing liquid ammonia from tail gas, primary hydrogen in the process of extracting hydrogen by pressure swing adsorption and secondary hydrogen and nitrogen in the process of copious cooling are added into a synthesis tower, an ammonia preparation catalyst is added to react to generate ammonia gas, liquid ammonia is formed by cooling treatment, primary hydrogen, secondary hydrogen and nitrogen are added into the synthesis tower to react in the technical process of preparing liquid ammonia from tail gas, and the catalyst used in the reaction process is FeO and Fe 2 O 3 And FeO and Fe 2 O 3 The mass ratio of (1) is 9, in the technical process of preparing liquid ammonia from tail gas, after multi-stage compression is carried out in the synthesis tower, the internal pressure of the synthesis tower is up to 32MPa, the temperature in the synthesis tower is controlled to be within the range of 480 ℃, in the technical process of preparing liquid ammonia from tail gas, most of water and hydrogen sulfide in crude ammonia gas are removed through three-stage segregation, and the conditions of the three-stage segregation are as follows: the primary segregation temperature is 170 ℃, and the pressure after segregation is 1.7MPa; the secondary segregation temperature is 130 ℃, and the pressure after segregation is 1.2MPa; the tertiary segregation temperature is 56 ℃, the pressure after segregation is 0.8MPa, the ammonia gas after segregation is cooled to-20 ℃, and the ammonia gas is converted into liquid ammonia.
EXAMPLE III
The invention provides a technical scheme that: a process for coproducing 1, 4-butanediol and liquid ammonia by coal gasification coupled with coal coking comprises the following steps:
the method comprises the following steps: the method comprises the following steps of (1) carrying out a raw gas purification process, wherein in the raw gas purification process, raw gas is firstly subjected to dust removal purification through dust removal equipment to obtain pretreated raw gas;
step two: a coal gasification process, wherein in the coal gasification process, coal powder is dried at the temperature of 100 ℃, then the coal powder is added into a gasification furnace, and a synthesis gas reaction is carried out at the pressure of 6KPa and the temperature of 1000 ℃ to generate primary carbon monoxide gas and primary hydrogen gas;
step three: in the pressure swing adsorption hydrogen extraction process, primary carbon monoxide gas is liquefied through temperature reduction treatment, and then primary hydrogen gas is separated;
step four: the raw coke oven gas conversion process comprises the following steps of conveying pretreated raw coke gas into a reaction tower, carrying out CO conversion reaction on the obtained coke oven gas and water vapor by using a conversion catalyst under the pressure conditions of 400 ℃ and 4MPa, converting CO in the coke oven gas and primary carbon monoxide gas to generate secondary hydrogen and generate secondary coke oven gas, wherein the conversion catalyst used in the raw coke gas conversion process is a Basff K8-11 sulfur-resistant conversion catalyst, and the mass ratio of the water vapor to the coke oven gas is as follows: 0.5;
step five: the method comprises the following steps of (1) carrying out decarburization reaction on secondary coke oven gas through a decarburization solvent in the decarburization process to obtain tertiary coke oven gas, wherein the decarburization solvent comprises 86wt% of a main agent, 12% of an activating agent and 2wt% of an auxiliary agent, the main agent comprises methyldiethanolamine and triethanolamine or methyldiethanolamine and diisopropylethanolamine, the activating agent is a mixture of primary amine and secondary amine, and the primary amine is hydroxyethyl ethylenediamine or 2-amino-2-methyl-1, 3-propanediol; the secondary amine is diethanolamine or methyl monoethanolamine, and the auxiliary agent comprises hydroxyethyl hexahydro-s-triazine and sodium sulfite;
step six: a methanation process, wherein in the methanation process, the tertiary coke oven gas is subjected to catalytic reaction under the action of a methanation catalyst to obtain CO and CO in the tertiary coke oven gas 2 The catalyst in the methanation process is a nickel-based catalystThe chemical matrix is Al 2 O 3 The catalyst promoter is La or Ce, and the catalyst contains 25wt% of nickel oxide, 5wt% of catalyst promoter and 70wt% of Al 2 O 3 ；
Step seven: a cryogenic process, wherein in the cryogenic process, after the mixed gas of methane obtained in the methanation process and the tertiary coke oven gas is dried and dehydrated, the mixed gas is liquefied at a temperature of minus 164 ℃ by using a mixed refrigerant, so as to produce liquid natural gas with the methane content of more than 98wt%, and meanwhile, secondary hydrogen and nitrogen which are byproducts are generated;
step eight: in the process of preparing acetylene by an oxidation method, liquid natural gas obtained by cryogenic technological process treatment is preheated to 720 ℃, then mixed in an acetylene cracking furnace mixer, and methane is partially oxidized and cracked at 1450 ℃ to obtain cracking gas containing acetylene;
step nine: in the BDO (acetylenic aldehyde method), separating primary acetylene gas from pyrolysis gas, purifying the primary acetylene gas to obtain secondary acetylene gas, using the secondary acetylene gas and formaldehyde as raw materials, generating 1, 4-butynediol under the action of a catalyst, adding the 1, 4-butynediol into a hydrogen reactor, and hydrogenating with hydrogen to generate a crude 1, 4-butanediol product, wherein in the BDO (acetylenic aldehyde method), in the BDO process, the reaction temperature is 70 ℃, the pressure is 2.2MPa, in the process of generating the 1, 4-butynediol by catalyzing the secondary acetylene gas and the formaldehyde, the reaction temperature is 135 ℃ and the pressure is 23MPa, and in the BDO process, the crude 1, 4-butanediol product obtained in the BDO process is separated, low-boiling-point impurities and most of water are firstly separated to obtain a 1, 4-butanediol solution with the concentration of 95 wt%; then removing a part of high-boiling-point residues from the 95wt% 1, 4-butanediol solution, recovering to obtain a high-purity 1, 4-butanediol solution, and further purifying to obtain a 1, 4-butanediol finished product with the final concentration of more than 99.5 wt%;
step ten: in the technical process of preparing liquid ammonia from tail gas and the technical process of preparing liquid ammonia from tail gas,adding primary hydrogen and secondary hydrogen and nitrogen in a cryogenic technological process in a pressure swing adsorption hydrogen extraction process into a synthesis tower, adding an ammonia preparation catalyst to react to generate ammonia, cooling to form liquid ammonia, adding the primary hydrogen, the secondary hydrogen and the nitrogen into the synthesis tower to react in a technological process of preparing the liquid ammonia from tail gas, wherein the catalyst used in the reaction process is FeO and Fe 2 O 3 And FeO and Fe 2 O 3 The mass ratio of (3) is 9, in the technical process of preparing liquid ammonia from tail gas, after multi-stage compression is carried out in the synthesis tower, the internal pressure of the synthesis tower is up to 32MPa, the temperature in the synthesis tower is controlled to be within the range of 480 ℃, in the technical process of preparing liquid ammonia from tail gas, most of water and hydrogen sulfide in crude ammonia are removed through three-stage segregation, and the conditions of the three-stage segregation are as follows: the primary segregation temperature is 170 ℃, and the pressure after segregation is 1.7MPa; the secondary segregation temperature is 130 ℃, and the pressure after segregation is 1.2MPa; the tertiary segregation temperature is 56 ℃, the pressure after segregation is 0.8MPa, the ammonia gas after segregation is cooled to-20 ℃, and the ammonia gas is converted into liquid ammonia.
Example four
The invention provides a technical scheme that: a process for coproducing 1, 4-butanediol and liquid ammonia by coal gasification coupled with coal coking comprises the following steps:
the method comprises the following steps: the method comprises the following steps of (1) carrying out a raw gas purification process, wherein in the raw gas purification process, raw gas is firstly subjected to dust removal purification through dust removal equipment to obtain pretreated raw gas;
step two: a coal gasification process, wherein in the coal gasification process, coal powder is dried at the temperature of 100 ℃, then the coal powder is added into a gasification furnace, and a synthesis gas reaction is carried out at the pressure of 6KPa and the temperature of 1000 ℃ to generate primary carbon monoxide gas and primary hydrogen gas;
step three: in the pressure swing adsorption hydrogen extraction process, primary carbon monoxide gas is liquefied through temperature reduction treatment, and then primary hydrogen gas is separated;
step four: the raw coke oven gas conversion process comprises the following steps of conveying pretreated raw coke gas into a reaction tower, carrying out CO conversion reaction on the obtained coke oven gas and water vapor by using a conversion catalyst under the pressure conditions of 400 ℃ and 4MPa, converting CO in the coke oven gas and primary carbon monoxide gas to generate secondary hydrogen and generate secondary coke oven gas, wherein the conversion catalyst used in the raw coke gas conversion process is a Basff K8-11 sulfur-resistant conversion catalyst, and the mass ratio of the water vapor to the coke oven gas is as follows: 0.5;
step five: the method comprises the following steps of (1) carrying out decarburization reaction on secondary coke oven gas through a decarburization solvent in the decarburization process to obtain tertiary coke oven gas, wherein the decarburization solvent comprises 89wt% of a main agent, 10% of an activating agent and 1wt% of an auxiliary agent, the main agent comprises methyldiethanolamine and triethanolamine or methyldiethanolamine and diisopropylethanolamine, the activating agent is a mixture of primary amine and secondary amine, and the primary amine is hydroxyethyl ethylenediamine or 2-amino-2-methyl-1, 3-propanediol; the secondary amine is diethanolamine or methyl monoethanolamine, and the auxiliary agent comprises hydroxyethyl hexahydro-s-triazine and sodium sulfite;
step six: the methanation process is that the three coke oven gases are subjected to catalytic reaction under the action of a methanation catalyst to react CO and CO in the three coke oven gases 2 The catalyst is nickel-based catalyst in the methanation process, and the catalyst substrate is Al 2 O 3 The catalyst promoter is La or Ce, and the catalyst contains 25wt% of nickel oxide, 5wt% of catalyst promoter and 70wt% of Al 2 O 3 ；
Step seven: a cryogenic process, wherein in the cryogenic process, after the mixed gas of methane obtained in the methanation process and the tertiary coke oven gas is dried and dehydrated, the mixed gas is liquefied at a temperature of minus 164 ℃ by using a mixed refrigerant, so as to produce liquid natural gas with the methane content of more than 98wt%, and meanwhile, secondary hydrogen and nitrogen which are byproducts are generated;
step eight: in the process of preparing acetylene by an oxidation method, liquid natural gas obtained by cryogenic technological process treatment is preheated to 720 ℃, then mixed in an acetylene cracking furnace mixer, and methane is partially oxidized and cracked at 1450 ℃ to obtain cracking gas containing acetylene;
step nine: in the BDO (acetylenic aldehyde method), separating primary acetylene gas from pyrolysis gas, purifying the primary acetylene gas to obtain secondary acetylene gas, using the secondary acetylene gas and formaldehyde as raw materials, generating 1, 4-butynediol under the action of a catalyst, adding the 1, 4-butynediol into a hydrogen reactor, and hydrogenating with hydrogen to generate a crude 1, 4-butanediol product, wherein in the BDO (acetylenic aldehyde method), in the BDO process, the reaction temperature is 70 ℃, the pressure is 2.2MPa, in the process of generating the 1, 4-butynediol by catalyzing the secondary acetylene gas and the formaldehyde, the reaction temperature is 135 ℃ and the pressure is 23MPa, and in the BDO process, the crude 1, 4-butanediol product obtained in the BDO process is separated, low-boiling-point impurities and most of water are firstly separated to obtain a 1, 4-butanediol solution with the concentration of 95 wt%; then removing a part of high-boiling-point residues from the 95wt% 1, 4-butanediol solution, recovering to obtain a high-purity 1, 4-butanediol solution, and further purifying to obtain a 1, 4-butanediol finished product with the final concentration of more than 99.5 wt%;
step ten: in the technical process of preparing liquid ammonia from tail gas, primary hydrogen in the process of extracting hydrogen by pressure swing adsorption and secondary hydrogen and nitrogen in the process of copious cooling are added into a synthesis tower, an ammonia preparation catalyst is added to react to generate ammonia gas, liquid ammonia is formed by cooling treatment, primary hydrogen, secondary hydrogen and nitrogen are added into the synthesis tower to react in the technical process of preparing liquid ammonia from tail gas, and the catalyst used in the reaction process is FeO and Fe 2 O 3 And FeO and Fe 2 O 3 The mass ratio of (3) is 9, in the technical process of preparing liquid ammonia from tail gas, after multi-stage compression is carried out in the synthesis tower, the internal pressure of the synthesis tower is up to 32MPa, the temperature in the synthesis tower is controlled to be within the range of 480 ℃, in the technical process of preparing liquid ammonia from tail gas, most of water and hydrogen sulfide in crude ammonia are removed through three-stage segregation, and the conditions of the three-stage segregation are as follows: the primary segregation temperature is 170 ℃, and the pressure after segregation is 1.7MPa; secondary segregation temperature 130 deg.C, segregationThe back pressure is 1.2MPa; the tertiary segregation temperature is 56 ℃, the pressure after segregation is 0.8MPa, the ammonia gas after segregation is cooled to-20 ℃, and the ammonia gas is converted into liquid ammonia.
Table one
Figure BDA0003931623510000131
Figure BDA0003931623510000141
Through the comparison experiment result of the four groups of examples and the comparative example, the decarburization efficiency of the coke oven gas can be obviously improved along with the increase of the usage percentage of the main agent, and the decarburization efficiency of the coke oven gas can be obviously improved along with the increase of the usage percentage of the activating agent and the auxiliary agent.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (10)

1. A coal gasification coupling coal coking coproduction process for preparing 1, 4-butanediol and liquid ammonia is characterized by comprising the following steps:
the method comprises the following steps: the method comprises the following steps of (1) raw gas purification, wherein in the raw gas purification, raw gas is subjected to dust removal purification through dust removal equipment to obtain pretreated raw gas;
step two: a coal gasification process, wherein in the coal gasification process, coal powder is dried at the temperature of 100 ℃, then the coal powder is added into a gasification furnace, and synthesis gas reaction is carried out at the pressure of 4-7 KPa and the temperature of 1000 ℃ to generate primary carbon monoxide gas and primary hydrogen gas;
step three: in the pressure swing adsorption hydrogen extraction process, primary carbon monoxide gas is liquefied through temperature reduction treatment, and then primary hydrogen gas is separated;
step four: the raw coke oven gas conversion process comprises the steps of conveying pretreated raw coke oven gas into a reaction tower, performing CO conversion reaction on the obtained coke oven gas and water vapor by using a conversion catalyst under the conditions of 190-480 ℃ and 3-5MPa, and then converting CO in the coke oven gas and primary carbon monoxide gas to generate secondary hydrogen and generate secondary coke oven gas;
step five: a decarburization process, wherein in the decarburization process, the secondary coke oven gas is subjected to decarburization reaction through a decarburization solvent to obtain a tertiary coke oven gas;
step six: performing a methanation process, wherein in the methanation process, the three times of coke oven gas are subjected to catalytic reaction under the action of a methanation catalyst to obtain CO and CO in the three times of coke oven gas 2 Converting into methane;
step seven: a cryogenic process, wherein in the cryogenic process, after the mixed gas of methane obtained in the methanation process and tertiary coke oven gas is dried and dehydrated, the mixed gas is liquefied at a temperature of between-165 and-162 ℃ by using a mixed refrigerant, so as to produce liquid natural gas with the methane content of more than 98wt%, and simultaneously generate secondary hydrogen and nitrogen as byproducts;
step eight: in the process of preparing acetylene by using an oxidation method, liquid natural gas obtained by cryogenic technological process treatment is preheated to 650-750 ℃, then is mixed in a mixer of an acetylene cracking furnace, and methane is partially oxidized and cracked at the temperature of 1300-1500 ℃ to obtain cracked gas containing acetylene;
step nine: in the process of preparing BDO by adopting an alkynal method, primary acetylene gas is separated from pyrolysis gas, the primary acetylene gas is purified to obtain secondary acetylene gas, the secondary acetylene gas and formaldehyde are used as raw materials, 1, 4-butynediol is generated under the action of a catalyst, and the 1, 4-butynediol is added into a hydrogen reactor and is hydrogenated with hydrogen to generate a crude 1, 4-butanediol product;
step ten: the technical process of preparing the liquid ammonia from the tail gas comprises the steps of adding primary hydrogen in a pressure swing adsorption hydrogen extraction process and secondary hydrogen and nitrogen in a cryogenic technological process into a synthesis tower, adding an ammonia preparation catalyst to react to generate ammonia gas, and cooling to form the liquid ammonia.
2. The process for coproduction of 1, 4-butanediol and liquid ammonia by coal gasification coupled with coal coking according to claim 1, which is characterized in that: the shift catalyst used in the raw coke oven gas shift process is a basf K8-11 sulfur-resistant shift catalyst, and the mass ratio of the water vapor to the coke oven gas is as follows: 0.4-0.5.
3. The process for coproduction of 1, 4-butanediol and liquid ammonia by coal gasification coupled with coal coking according to claim 1, which is characterized in that: the decarbonization solvent comprises 80-91 wt% of a main agent, 5-16 wt% of an activating agent and 0.75-4 wt% of an auxiliary agent.
4. The process for coproduction of 1, 4-butanediol and liquid ammonia by coal gasification coupled with coal coking according to claim 3, which is characterized in that: the main agent comprises methyldiethanolamine and triethanolamine or methyldiethanolamine and diisopropylethanolamine, the activating agent is a mixture of primary amine and secondary amine, and the primary amine is hydroxyethyl ethylenediamine or 2-amino-2-methyl-1, 3-propanediol; the secondary amine is diethanolamine or methyl monoethanolamine, and the auxiliary agent comprises hydroxyethyl hexahydro-s-triazine and sodium sulfite.
5. The process for coproduction of 1, 4-butanediol and liquid ammonia by coal gasification coupled with coal coking according to claim 1, which is characterized in that: the catalyst in the methanation process is a nickel-based catalyst, and the catalyst substrate is Al 2 O 3 The catalyst assistant is La or Ce, the catalyst contains 20-30 wt% of nickel oxide and 4-6 wt% of catalyst assistantAnd 64wt% to 76wt% of Al 2 O 3 。
6. The process for coproduction of 1, 4-butanediol and liquid ammonia by coal gasification coupled with coal coking according to claim 1, which is characterized in that: in the process of preparing BDO by the alkynal method, in the process of separating acetylene gas from pyrolysis gas, the reaction temperature is 50-75 ℃, and the pressure is 1.5-2.5 MPa, and in the process of catalyzing secondary acetylene gas and formaldehyde to generate 1, 4-butynediol, the reaction temperature is 120-150 ℃, and the pressure is 15-25 MPa.
7. The process for coproduction of 1, 4-butanediol and liquid ammonia by coal gasification coupled with coal coking according to claim 6, wherein: firstly, separating low-boiling-point impurities and most of water from a crude 1, 4-butanediol product obtained in the BDO preparation process by using an alkynal method to obtain a 1, 4-butanediol solution with the concentration of 95 wt%; then removing a part of high-boiling-point residues from the 95wt% 1, 4-butanediol solution, recovering to obtain a high-purity 1, 4-butanediol solution, and further purifying to obtain a 1, 4-butanediol finished product with the final concentration of more than 99.5 wt%.
8. The process for coproduction of 1, 4-butanediol and liquid ammonia by coal gasification coupled with coal coking according to claim 1, which is characterized in that: in the technical process of preparing liquid ammonia from tail gas, primary hydrogen, secondary hydrogen and nitrogen are added into a synthesis tower for reaction, and catalysts used in the reaction process are FeO and Fe 2 O 3 And FeO and Fe 2 O 3 The mass ratio of (1) is 9.
9. The process for coproduction of 1, 4-butanediol and liquid ammonia by coal gasification coupled with coal coking according to claim 8, wherein the process comprises the following steps: in the process of preparing liquid ammonia from tail gas, after multi-stage compression is carried out in the synthesis tower, the internal pressure of the synthesis tower reaches 32MPa, and the temperature in the synthesis tower is controlled within the range of 450-500 ℃.
10. The process for coproduction of 1, 4-butanediol and liquid ammonia by coal gasification coupled with coal coking according to claim 9, which is characterized in that: in the technical process of preparing liquid ammonia from tail gas, most of water and hydrogen sulfide in the crude ammonia gas are removed through three-stage segregation, and the conditions of the three-stage segregation are as follows: the first-stage segregation temperature is 120-200 ℃, and the pressure after segregation is 0.6-2.0 MPa; the secondary segregation temperature is 90-150 ℃, and the pressure after segregation is 0.55-1.5 MPa; the tertiary segregation temperature is 30-70 ℃, the pressure after segregation is 0.5-1.0 MPa, the ammonia gas after segregation is cooled to-30-20 ℃, and the ammonia gas is converted into liquid ammonia.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105154121A (en) * 2015-10-15 2015-12-16 上海锅炉厂有限公司 Low-rank coal gradation usage poly-generation system and method
CN114149837A (en) * 2021-10-29 2022-03-08 西南化工研究设计院有限公司 Process for preparing liquefied natural gas and co-producing liquid ammonia or hydrogen by coke oven gas with conversion decarburization
CN114409503A (en) * 2021-11-23 2022-04-29 中国平煤神马能源化工集团有限责任公司 Process for preparing BDO and co-producing liquid ammonia by using coke oven gas
CN114591771A (en) * 2022-03-28 2022-06-07 中国石油大学(北京) Decarbonizing solvent and method for decarbonizing high carbon-containing natural gas

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105154121A (en) * 2015-10-15 2015-12-16 上海锅炉厂有限公司 Low-rank coal gradation usage poly-generation system and method
CN114149837A (en) * 2021-10-29 2022-03-08 西南化工研究设计院有限公司 Process for preparing liquefied natural gas and co-producing liquid ammonia or hydrogen by coke oven gas with conversion decarburization
CN114409503A (en) * 2021-11-23 2022-04-29 中国平煤神马能源化工集团有限责任公司 Process for preparing BDO and co-producing liquid ammonia by using coke oven gas
CN114591771A (en) * 2022-03-28 2022-06-07 中国石油大学(北京) Decarbonizing solvent and method for decarbonizing high carbon-containing natural gas

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