CN110760338A - Method for producing series products by using Fischer-Tropsch synthesis hydrogenation products - Google Patents

Method for producing series products by using Fischer-Tropsch synthesis hydrogenation products Download PDF

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Publication number
CN110760338A
CN110760338A CN201810852017.8A CN201810852017A CN110760338A CN 110760338 A CN110760338 A CN 110760338A CN 201810852017 A CN201810852017 A CN 201810852017A CN 110760338 A CN110760338 A CN 110760338A
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temperature
fraction
fischer
products
series
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苗恒
潘金亮
李俊诚
郭良兰
周岩
郑会月
马国清
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Inner Mongolia Yitai Coal Based New Materials Research Institute Co Ltd
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Inner Mongolia Yitai Coal Based New Materials Research Institute Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G73/00Recovery or refining of mineral waxes, e.g. montan wax
    • C10G73/42Refining of petroleum waxes
    • C10G73/44Refining of petroleum waxes in the presence of hydrogen or hydrogen-generating compounds

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A method for producing a series of products by using hydrogenation products of Fischer-Tropsch synthesis comprises the following steps: hydrofining the intermediate product of Fischer-Tropsch synthesis to obtain a hydrogenated product of Fischer-Tropsch synthesis; according to the distillation range of a target product, preliminarily separating the hydrogenation product of the Fischer-Tropsch synthesis into a plurality of wide fractions containing the target distillation range; carrying out precision separation on the wide fraction to obtain a series of narrow fractions; directly taking the series of narrow fractions as products, or physically or chemically modifying the series of narrow fractions to obtain final products; wherein the preliminary separation comprises atmospheric fractionation and vacuum fractionation, and the precise separation comprises vacuum rectification, molecular short-path distillation or thin film distillation. The production process is simple, customized production can be realized as required, the raw materials are fully utilized, waste is reduced, cost is reduced, and economic benefits are effectively improved.

Description

Method for producing series products by using Fischer-Tropsch synthesis hydrogenation products
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a method for producing series products by Fischer-Tropsch synthesis hydrogenation products.
Background
The Fischer-Tropsch synthesis product is a methylene polymer, and is an alkane mixture obtained by catalytic polymerization reaction of synthesis gas at medium temperature and medium pressure, a small amount of olefin in the saturated Fischer-Tropsch synthesis product is subjected to hydrofining, a small amount of oxygen-containing organic matters in the saturated Fischer-Tropsch synthesis product and a small amount of polycyclic hydrocarbon in the hydrogenated chain-broken Fischer-Tropsch synthesis product are reduced, the content of straight-chain alkane in the Fischer-Tropsch synthesis hydrogenation product can reach over 90 percent, the rest is mainly branched-chain alkane, and the branched-chain alkane is basically free of cyclic hydrocarbon and aromatic hydrocarbon.
The distillation range of each brand dearomatization solvent oil product is mainly concentrated in the range of 120-plus-300 ℃, the low-temperature phase change wax product is mainly concentrated in the range of 300-plus-390 ℃, and the fraction above 390 ℃ can produce each brand Fischer-Tropsch wax product, and is widely applied to the fields of candle production, wood processing, rubber protection, PVC processing, hot melt adhesive, ink coating and the like. The distillation range of the normal paraffin required by the alkylbenzene raw material is centralized in the range of 170-240 ℃, and the distillation range of the normal paraffin required by the environment-friendly chlorinated paraffin is in the range of 240-300 ℃. According to the distillation range requirement of the normal paraffin required by the downstream product, preliminarily separating the hydrogenated Fischer-Tropsch synthesis product to obtain a fraction with the temperature of less than 160 ℃, a fraction with the temperature of 160 ℃ and 300 ℃, a fraction with the temperature of 300 ℃ and 400 ℃ and a wide fraction with the temperature of more than 400 ℃, and precisely separating the wide fraction according to the precision requirement of the distillation range of the target product to obtain a continuous narrow fraction product. And (3) performing distillation separation on the fraction below 160 ℃ to obtain a narrow fraction with the distillation range of 30-40 ℃, such as separated 60-90 ℃ as 6# solvent oil, 90-120 ℃ as 120# solvent oil, 120-160 ℃ as D30 solvent oil, or precisely separating the fraction below 160 ℃ to obtain products such as n-pentane, n-hexane, n-heptane and the like. After the distillation of the 160-DEG C and 300-DEG C fractions, obtaining a 160-DEG C and 240-DEG C alkylbenzene raw material, a 240-DEG C and 300-DEG C environment-friendly chlorinated paraffin raw material and an oil displacement agent raw material; the 300-plus 400 ℃ fraction is subjected to precise separation to obtain a continuous narrow fraction section with the distillation range of 20-60 ℃, and a series of low-temperature phase-change wax products, high-grade chlorinated paraffin raw materials, cosmetic base materials and the like can be produced after further refining; the fractions above 400 ℃ are precisely separated to obtain continuous narrow-cut sections with the distillation range of 30-80 ℃, thus producing Fischer-Tropsch wax with the brands of 50#, 60#, 70#, 80#, 90#, 100#, 105 and 110# and the like, and the Fischer-Tropsch wax with each brand can be directly used as a product or be subjected to physical and chemical modification to obtain various special wax products, and can be widely used in the fields of process candles, emulsified wax, wood processing, rubber and plastic processing, rubber protection, PVC processing, ink and paint and the like.
In the prior art, separation by taking Fischer-Tropsch refined wax as a raw material is reported, but the separation of other Fischer-Tropsch hydrogenation materials is only reported. In the prior art, a method for processing Fischer-Tropsch wax to produce series products is provided, and Fischer-Tropsch refined wax in a Fischer-Tropsch hydrogenation product is used as a raw material, and various grades of wax products are produced through separation and modification. The technology is only used for separating the Fischer-Tropsch refined wax, the raw materials are primarily separated into light and heavy component materials, the raw materials are separated widely, targeted separation is not carried out according to the distillation range of a target product, and the operation cost of subsequent precise separation is increased.
Disclosure of Invention
Aiming at the defects of the prior art, the method is used for separating the whole fraction of the Fischer-Tropsch hydrogenation product according to the unique advantages of the Fischer-Tropsch hydrogenation product for producing the unique chemicals. The method comprises the steps of performing primary separation according to the distillation range of a target series product to separate wider components, then performing precise separation according to the index requirement of the target product to obtain narrow fraction, wherein the narrow fraction can be directly used as a product or can be subjected to physicochemical modification to obtain a final product, the fractional collection of the distillation range above 10 ℃ can be realized, and the separation of the whole fraction of the Fischer-Tropsch synthesis product can be realized.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for producing a series of products by using hydrogenation products of Fischer-Tropsch synthesis comprises the following steps:
hydrofining the intermediate product of Fischer-Tropsch synthesis to obtain a hydrogenated product of Fischer-Tropsch synthesis;
according to the distillation range of a target product, preliminarily separating the hydrogenation product of the Fischer-Tropsch synthesis into a plurality of wide fractions containing the target distillation range;
carrying out precision separation on the wide fraction to obtain a series of narrow fractions;
directly taking the series of narrow fractions as products or physically or chemically modifying the series of narrow fractions to form final products;
wherein the preliminary separation comprises atmospheric fractionation and vacuum fractionation, and the precise separation comprises vacuum rectification, a thin film evaporator or a short-path evaporator.
Preferably, the hydrofining operation temperature is 240-340 ℃, and the operation pressure is 3-10 MPa.
Preferably, the preliminary separation comprises first an atmospheric fractionation followed by a vacuum fractionation.
Preferably, in the atmospheric fractionation, the feeding temperature of the atmospheric fractionation tower is 280-320 ℃, the overhead temperature is 90-115 ℃, and the fraction at the temperature lower than 160 ℃ is extracted from the overhead; the side line extraction temperature is 170-190 ℃, the side line extraction temperature is 160-300 ℃, and the bottom product of the normal pressure fractionation enters a reduced pressure fractionation tower; in the vacuum fractionation, the operating pressure of the vacuum fractionating tower is 10-50KPa, the temperature at the top of the tower is 100-150 ℃, the fraction at the top of the tower is extracted at the temperature of less than 300 ℃, the fraction is merged into the fraction at the temperature of 160-300 ℃ extracted by the side line of the normal pressure tower, the temperature at the side line is controlled at 300 ℃, the fraction at the temperature of 300-400 ℃ extracted by the side line is extracted, and the bottom product of the vacuum fractionating tower is used as the fraction at the temperature of more than 400 ℃.
Preferably, the precise separation adopts a vacuum rectification tower, a vacuum rectification tower with a side line, a vacuum rectification tower group or a short-path evaporator; preferably, the operating pressure of the precise separation is 0-50KPa, and the operating temperature is 80-350 ℃.
Preferably, when the fraction above 400 ℃ is precisely separated, the operating pressure is 1-100Pa, the operating temperature is 100-330 ℃, and a series of narrow fractions with the distillation range of 30-80 ℃ are separated.
Preferably, when the fraction at 400 ℃ and 300 ℃ is precisely separated, the operating pressure is 0.5-5KPa, the operating temperature is 100 ℃ and 280 ℃, and a series of narrow fractions with the distillation range of 20-60 ℃ are separated.
Preferably, when the 160-300 ℃ fraction is precisely separated, the operation pressure is 10-30KPa, the tower top temperature is 120-190 ℃ to extract the 160-240 ℃ fraction, and the remainder is 240-300 ℃ fraction.
Preferably, the physical modification comprises blending with the addition of at least one of paraffin wax, microcrystalline wax, low density polyethylene wax, polypropylene, or blending between the narrow fractions.
Preferably, the chemical modification includes any one of oxidation modification, emulsification modification, chlorination modification, esterification modification, or saponification modification.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
1. the invention selects the coal-based Fischer-Tropsch hydrogenation product as the raw material, has simple group composition, has the normal straight-chain alkane content of more than 90 percent, basically contains branched-chain alkane as the rest, basically does not contain cyclic hydrocarbon and aromatic hydrocarbon, and improves the normal hydrocarbon content without solvent dewaxing compared with the petroleum wax raw material; meanwhile, the material has stable chemical properties, no corrosiveness and no environmental pollution, and is an excellent raw material for producing special chemicals. The invention aims at the special advantages of the coal-based Fischer-Tropsch hydrogenation product, and has various raw materials and abundant products.
2. According to the characteristics of the target product, the primary separation is carried out, and then the precise separation is carried out. Compared with the method for directly and precisely separating the Fischer-Tropsch product, the method has the advantages that the operation cost is reduced, and the separation precision of the final product can be improved so as to improve the product quality.
3. The invention has simple production process and flexible product, and can realize customized production according to the requirement; meanwhile, the raw materials are fully utilized, the waste is reduced, the cost is reduced, and the economic benefit is effectively improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments.
The invention provides a method for producing series products by using a Fischer-Tropsch synthesis product, which comprises the steps of preliminarily separating the hydrofined Fischer-Tropsch synthesis product according to the distillation range of a target product to obtain a wide fraction containing the target distillation range, further separating the wide fraction product to obtain a continuous series of narrow fractions with the distillation range of 10-80 ℃, and finally separating the full fraction of the Fischer-Tropsch synthesis product to achieve the purpose of comprehensively utilizing raw materials, wherein the narrow fractions can be directly used as the target product or used as the final product after physicochemical modification.
The coal-based Fischer-Tropsch synthesis intermediate product (comprising light distillate oil, heavy distillate oil and Fischer-Tropsch wax) is subjected to hydrogenation reaction, wherein the operation temperature of the hydrogenation reaction is 240-340 ℃, the operation pressure is 3-10MPa, and the aim of hydrofining is to hydrogenate a small amount of olefins in saturated Fischer-Tropsch synthesis intermediate product, hydrogenate a small amount of oxygen-containing organic matters in reduced Fischer-Tropsch synthesis intermediate product and hydrogenate a small amount of polycyclic hydrocarbons in chain scission Fischer-Tropsch synthesis intermediate product. If the substances are not removed, the chromaticity of products separated from the Fischer-Tropsch intermediate products is influenced, and on the other hand, coking and carbon deposition are easily generated in subsequent processing treatment, so that the quality and normal production of the products are influenced.
The Fischer-Tropsch synthesis hydrogenation product is subjected to normal pressure and reduced pressure fractionation to realize primary separation, and fractions with the temperature of less than 160 ℃, 160 ℃ and 300 ℃ and 400 ℃ and above 400 ℃ are separated. And each wide fraction section is further separated into a series of narrow fraction sections by a precise separation device according to the target product index.
The precise separation is carried out in any one of the following separation devices: comprises a vacuum rectification tower, a vacuum rectification tower with a lateral line, a vacuum rectification tower group and a short-path evaporator; the operating pressure of the separation equipment is 0-50KPa, and the operating temperature is 80-350 ℃.
Example 1
The method comprises the steps of taking a certain coal-based Fischer-Tropsch synthesis intermediate product (comprising light distillate oil, heavy distillate oil and Fischer-Tropsch wax) as a raw material, and introducing the product into an atmospheric and vacuum fractionating tower after hydrofining to obtain fractions with the temperature of less than 160 ℃, 160 ℃ and 300 ℃, 300 ℃ and 400 ℃ and above 400 ℃ after fractionation. The hydrofining temperature is 280 ℃, and the reaction pressure is 6 MPa; the feeding temperature of the atmospheric fractionating tower is 300 ℃, the temperature at the top of the tower is controlled to be 95-105 ℃, and the fraction below 160 ℃ is extracted from the top of the tower; the side line extraction temperature is 175-; the bottom product of the atmospheric tower enters a vacuum tower, the pressure of the vacuum tower is controlled to be 20KPa, the temperature of the top of the vacuum tower is controlled to be 120-150 ℃, the fraction of which the temperature is lower than 300 ℃ is extracted from the top of the vacuum tower and is merged into the fraction of which the temperature is 160-300 ℃ extracted from the side line of the atmospheric tower. The side draw temperature is controlled at 280 ℃ and 300 ℃, and the side draw temperature is controlled at 300 ℃ and 400 ℃. The vacuum bottoms were taken as a > 400 ℃ fraction.
Passing the fraction above 400 deg.C through a pressure-reducing separation device, operating pressure is 5Pa, operating temperature is raised gradually from 140 deg.C to 350 deg.C, and separating out a series of narrow fractions with distillation range of 50 deg.C.
The fractions can be used as Fischer-Tropsch wax products of No. 60, No. 65, No. 70, No. 75, No. 80, No. 90, No. 95, No. 100, No. 105 and No. 110 according to melting points, and special wax products such as candle light special wax, rubber protective wax, high-temperature phase change wax, PVC processing special wax, asphalt synergistic wax and the like can also be obtained through physical and chemical modification.
The physical modification is that at least one of paraffin, microcrystalline wax, low-density polyethylene wax, polypropylene and the like is added into the material for blending, or all the fractions are blended with each other. The chemical modification is any one of oxidation modification, emulsification, chlorination, esterification or saponification modification.
Example 2
Taking the fraction of 300-400 ℃ as a raw material, passing through a reduced pressure rectification device, wherein the operating pressure is 1KPa, the operating temperature is gradually increased from 150 ℃ to 240 ℃, and a series of narrow fractions with the distillation range of 30 ℃ are separated. The fractions can be used as Fischer-Tropsch wax products of No. 20, No. 25, No. 30, No. 35, No. 40, No. 45, No. 50 and No. 55 according to melting points. Or can be modified by physical chemistry to obtain phase-change wax, candle special wax, food and medical wax, high-grade chlorinated paraffin and other special wax products.
Example 3
The 160-plus 300 ℃ fraction is taken as a raw material, the operating pressure is set to be 20KPa by a vacuum rectification device, the 160-plus 240 ℃ fraction is extracted at the tower top temperature of 120-plus 190 ℃, and the remainder is the 240-plus 300 ℃ fraction which can be respectively used as a raw material for producing alkylbenzene and an environment-friendly chlorinated paraffin or an oil displacement agent. Alkylbenzenes are used in the production of surfactants and synthetic detergents. The chlorinated paraffin is used for producing products such as cable materials, floor plates, hoses, artificial leather, rubber and the like and is applied to additives such as coatings, lubricating oil and the like.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A method for producing a series of products by using hydrogenation products of Fischer-Tropsch synthesis comprises the following steps:
hydrofining the intermediate product of Fischer-Tropsch synthesis to obtain a hydrogenated product of Fischer-Tropsch synthesis;
according to the distillation range of a target product, preliminarily separating the hydrogenation product of the Fischer-Tropsch synthesis into a plurality of wide fractions containing the target distillation range;
carrying out precision separation on the wide fraction to obtain a series of narrow fractions;
directly taking the series of narrow fractions as products or physically or chemically modifying the series of narrow fractions to form final products;
wherein the preliminary separation comprises atmospheric fractionation and vacuum fractionation, and the precise separation comprises vacuum rectification, molecular short-path distillation or thin film distillation.
2. The method as claimed in claim 1, wherein the hydrofinishing is carried out at an operating temperature of 240-340 ℃ and an operating pressure of 3-10 MPa.
3. The method of claim 1, wherein the preliminary separation comprises first atmospheric fractionation followed by vacuum fractionation.
4. The process as claimed in claim 1, wherein in the atmospheric fractionation, the feed temperature of the atmospheric fractionating tower is 280-320 ℃, the overhead temperature is 90-115 ℃, and the fraction at < 160 ℃ is extracted from the overhead; the side line extraction temperature is 170-190 ℃, the side line extraction temperature is 160-300 ℃, and the bottom product of the normal pressure fractionation enters a reduced pressure fractionation tower; in the vacuum fractionation, the operating pressure of the vacuum fractionating tower is 10-50KPa, the temperature at the top of the tower is 100-150 ℃, the fraction at the top of the tower is extracted at the temperature of less than 300 ℃, the fraction is merged into the fraction at the temperature of 160-300 ℃ extracted by the side line of the normal pressure tower, the temperature at the side line is controlled at 300 ℃, the fraction at the temperature of 300-400 ℃ extracted by the side line is extracted, and the bottom product of the vacuum fractionating tower is used as the fraction at the temperature of more than 400 ℃.
5. The method according to claim 1, wherein the precise separation adopts a vacuum rectification tower, a vacuum rectification tower with a side line, a vacuum rectification tower group, a molecular short-path evaporator or a thin film evaporator; preferably, the operating pressure of the precise separation is 0-50KPa, and the operating temperature is 80-350 ℃.
6. A process according to claim 4, wherein the precise separation of the fractions above 400 ℃ is carried out at an operating pressure of 1 to 100Pa, at an operating temperature of 100 ℃ to 350 ℃ and in a series of narrow fractions having a distillation range of 30 to 80 ℃.
7. The process as claimed in claim 4, wherein the precise separation of the 300-400 ℃ fraction is carried out at an operating pressure of 0.5-5KPa and an operating temperature of 100-280 ℃ to separate a series of narrow fractions having a distillation range of 20-60 ℃.
8. The method as claimed in claim 4, wherein the operation pressure is 10-30KPa, the column top temperature is 120-190 ℃ to extract the 160-300 ℃ fraction, and the remainder is the 240-300 ℃ fraction.
9. The method of claim 1, wherein the physical modification comprises blending with the addition of at least one of paraffin wax, microcrystalline wax, low density polyethylene wax, polypropylene, or blending between the narrow fractions.
10. The method of claim 1, wherein the chemical modification comprises any of an oxidative modification, an emulsification modification, a chlorination modification, an esterification modification, or a saponification modification.
CN201810852017.8A 2018-07-27 2018-07-27 Method for producing series products by using Fischer-Tropsch synthesis hydrogenation products Pending CN110760338A (en)

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Cited By (2)

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CN111234870A (en) * 2020-02-14 2020-06-05 国家能源集团宁夏煤业有限责任公司 Utilization method of Fischer-Tropsch synthesis product
CN111996036A (en) * 2020-08-20 2020-11-27 北京明星绿能化工科技有限公司 Preparation equipment and preparation method of series of high phase-change enthalpy value phase-change waxes

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CN111234870A (en) * 2020-02-14 2020-06-05 国家能源集团宁夏煤业有限责任公司 Utilization method of Fischer-Tropsch synthesis product
CN111996036A (en) * 2020-08-20 2020-11-27 北京明星绿能化工科技有限公司 Preparation equipment and preparation method of series of high phase-change enthalpy value phase-change waxes

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