CN1648112A - Process to make a sulphur containing steam cracker feedstock - Google Patents

Process to make a sulphur containing steam cracker feedstock Download PDF

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Publication number
CN1648112A
CN1648112A CNA2004100104986A CN200410010498A CN1648112A CN 1648112 A CN1648112 A CN 1648112A CN A2004100104986 A CNA2004100104986 A CN A2004100104986A CN 200410010498 A CN200410010498 A CN 200410010498A CN 1648112 A CN1648112 A CN 1648112A
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China
Prior art keywords
gas
steam cracker
hydrocarbon
obtains
feed stock
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CNA2004100104986A
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Chinese (zh)
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CN100430347C (en
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G·J·范赫尔林根
A·S·艾德鲁斯
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • 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
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/34—Purifying combustible gases containing carbon monoxide by catalytic conversion of impurities to more readily removable materials
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
    • C10L2230/14—Function and purpose of a components of a fuel or the composition as a whole for improving storage or transport of the fuel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/06—Heat exchange, direct or indirect
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/42—Fischer-Tropsch steps

Abstract

The method for producing a sulfur-containing steam cracker feedstock from a crude natural gas comprises the steps of (a) separating a sulfur-containing liquid gas field condensate fraction from a crude natural gas, (b) dividing the liquid gas field condensate into a high-boiling fraction and a low-boiling fraction, (c) producing a carbon monoxide/hydrogen mixture from the gas obtained from step (a), (d) producing a paraffin product by performing a Fischer-Tropsch reaction by using the carbon monoxide and the hydrogen from step (c), and (e) obtaining the sulfur-containing steam cracker feedstock of a sulfur content of 50 to 1,000 ppm by blending at least part of the paraffin product with the low-boiling fraction obtained in step (b).

Description

The method of the steam cracker feed stock of preparation sulfur-bearing
Technical field
The present invention relates to be equipped with by gas material the method for the steam cracker feed stock of sulfur-bearing by the sulfur-bearing material combination in the paraffinic feed that will obtain in the Fischer-Tropsch process and another source.
Background technology
Technician in the steam cracker method and technology field knows and sulphur is added raw material can reduce coke and generate.Coke in steam cracker furnace tubes generates main by two kinds of mechanism, i.e. pyrolysis reaction and catalytic dehydrogenating reaction.By with low operating pressure, have the ratio of high steam and hydrocarbon about 30% to 60%, and avoid the metal tube temperature too high and avoid making unevaporated raw material to enter the high-temperature zone, thereby pyrolytic reaction minimized.In order to tolerate pipe metallic high temperature, use to contain nickelic and alloy chromium, as contain the alloy of 35% nickel and 25% chromium up to 2100.Therefore these metal catalytic dehydrogenation reactions need make its passivation.Sulfuration is typical passivating method.A kind of conventional process for steam cracker operation person is exactly just to add coking inhibitor after the decoking operation.Just when tube wall metal catalytic activity is the strongest.Before stove that hydrocarbon feed is packed into, DMS or DMDS are injected spirally coiled sulphidisation film with steam.For typical liquid starting material, sulphur content enough maintains the sulfide level in the actual steam cracking process usually in the raw material.If in raw material, do not had enough sulphur, then sulphur can have been joined in the raw material.In this case, add about 20ppm minimizes coke and CO to the sulphur of 100ppm generation.
Also know naphtha paraffin product that use obtains in addition as steam cracker feed stock in Fischer-Tropsch process.For example, the Peter J.A.Tijm of Shell International Gas Ltd. is at AlternativeEnergy ' 95 ' Vancouver, Canada, May 2-4, mention naphtha fraction SMDS petroleum naphtha that the Fischer-Tropsch process that uses Shell MDS technology obtains on report on 1995 " the The Markets for ShellMiddle Distillate Synthesis Products " page 5 as steam cracker feed stock, for example in Singapore.
, before can be, must in this raw material, add sulphur used as steam cracker feed stock because but the product that Fischer-Tropsch process obtains contains the sulphur of detection level hardly.By adding the sulfur additives as dimethyl disulfide (DMDS) or accomplishing this point, in saving, " Preliminary Survey on GTLBusiness Based on SMDS technology " 6.2.3 describes in detail as Japan External Trade Organizat ion in June calendar year 2001 (JETRO) by the fischer-tropsch raw material is mixed with the high sulfur content raw material.
In nearest disclosed patent publications US-A-2003/0135077, also described in steam cracker and sulphur to have been joined fischer-tropsch and think of a way in the raw material that obtains.This publication has been described and has been produced the petroleum naphtha that the low-sulfur Fischer-Tropsch process obtains in the side area, use described petroleum naphtha as steam cracker feed stock before, this product is transported to the place of steam cracker and sulfide is joined in the petroleum naphtha.
WO-A-9937736 discloses hydrotreatment by the method for the isolating oil field of raw natural gas condensation product with reduction sulphur level.According to the disclosure content, need to remove desulfuration to make fuel with it or to mix with other hydrocarbon and as the raw material of chemical technology.
The shortcoming of the method for WO-A-9937736 is to need additional hydrotreatment unit.
Summary of the invention
The objective of the invention is to prepare the steam cracker feed stock of sulfur-bearing by Sweet natural gas.
Realize this purpose by following method.Prepare the method for the steam cracker feed stock of sulfur-bearing by dirt gas, wherein carry out following steps:
(a) the liquid oil field condensation product cut of separate sulphur from Sweet natural gas,
(b) from Sweet natural gas, further separate the sour distillate that comprises hydrocarbon compound and obtain the process condensate thing with 3 or more a plurality of carbon atoms,
(c) prepare the mixture of carbon monoxide and hydrogen by the gas that obtains in the step (b),
(d) by be used to from the carbon monoxide of (c) step and hydrogen carry out Fischer-Tropsch reaction prepare paraffin products and
(e) comprising of obtaining in described paraffin products or described portioned product and the step (b) had 3 or the sour distillate of the hydrocarbon compound of more a plurality of carbon atoms mix, obtain the sulfur-bearing steam cracker feed stock.
The applicant has been found that the method according to this invention can advantageously will separate the portion C 3+ compound that obtains by Sweet natural gas and mix with the paraffin products that utilizes Fischer-Tropsch process to obtain.Application goes into to find that this logistics helps increasing steam cracker feed stock volume and sulphur content thereof, therefore makes it become the fabulous steam cracker feed stock that direct use technology requires that satisfies.This is favourable, because it has saved the oil depot facility at the Fischer-Tropsch process production site, and a kind of product rather than two kinds of products that separate can be transported to the overseas customer.
Embodiment
Can carry out step (a) according to the method for knowing.Typically, from missile silo, obtain Sweet natural gas.After gas arrives ground typically with the hydrocarbon gas and the C of 1-5 carbon atom 5+ hydrocarbon separates, and for example separates in so-called material (slug) trap.The liquid product that obtains like this is also referred to as the oil field condensation product, and may have very high sulphur level, for example more than 1500ppm, even more than 1900ppm.Typical lower level is a 1000ppm sulphur.The Sweet natural gas of wherein isolating the oil field condensation product is called the precleaning Sweet natural gas.
May have very high full boiling point by this liquid condensate that obtains in the step (a), even be higher than 300 ℃, but most of products are being lower than 300 ℃ of boilings down simultaneously.Preferably isolate high boiling fraction, just obtain comprising sulphur compound and the satisfied low boiler cut that is used as the boiling spread requirement of steam cracker feed stock by for example flash distillation step or distilation steps.This cut needn't be further removes sulphuring treatment and just can be used as in the step (e) additional combined group assign to prepare steam cracker feed stock in the preferred embodiment of the invention.Isolated this low boiler cut preferably has the full boiling point between 120-230 ℃ from the condensation product of oil field, more preferably between 140-215 ℃.Initial boiling point and the C that still is present in the condensation product of liquid oil field 5The hydrocarbon correspondence.The full boiling point of low boiler cut can be with the sulphur content in the condensation product of oil field, in step (b) with the variation of the sulphur level of the final mixture of the ratio of mixture of the cut that obtains (a) and fischer-tropsch products in step (e) and expectation.Can utilize ordinary skill to determine optimum operation.Be rich in sulfide and organic acid high boiling fraction, can further process in so-called local condensation product refinery.Low boiler cut preferably comprises the sulphur of 200-6000ppm.
It is preceding to carry out step (b), isolates most of sulphur in the precleaning Sweet natural gas that obtains from step (a) by various possible technology.Preferably from Sweet natural gas, remove coloured glaze by so-called absorption type method.These methods of knowing comprise the step that Sweet natural gas is contacted with the liquid mixture that contains physics and chemical absorber.In this method, in two steps, under high pressure handle gaseous mixture with two kinds of different liquid mixtures that comprise physical absorbent and chemical absorber continuously.Typical chemical absorber is a tertiary amine, particularly wherein comprises the tertiary amine of at least one hydroxyalkyl.Trolamine, diethylethanolamine (DEMEA) and methyldiethanolamine (MDEA) are fit closely.Typical physical absorbent is Texacar PC N-methyl arsenic pyrrolidone, dimethyl formamide, Polyethylene glycol dimethyl ether.Tetraethylene glycol dimethyl ether and tetramethylene sulfone are fit closely.At US-A-4372925 with at textbook such as Gas Purification, 5th ed./Arthur Kohl and RichardNielsen, 1997, Gulf Publishing Company all describes the example of these class methods in detail in ISBN 0-88415-220-0 the 1st chapter.
Before converting gas to synthetic gas, in step (b), will have 3 or the hydrocarbon compound of more a plurality of carbon atoms from Sweet natural gas, separate.Preferably by gas cooling is separated under the temperature and pressure condition of these hydrocarbon liquefaction.Then can be easily that liquid product is separated from the gas.Can be preferably by cooling off by the liquid nitrogen indirect heat exchange.The excess nitrogen that liquid nitrogen preferably can obtain when obtaining being used for step (c) pure oxygen for separation of air.Preferred method be utilize gas prepare synthetic gas before by reducing the C of pressure, separating and condensing 3+ hydrocarbon and optional rising stress level.Preferably gas is reduced to the pressure that is lower than 40 crust from the pressure that surpasses 50 crust, preferably is lower than 30 crust.At the liquid hydrocarbon after separating, gaseous tension is increased to the level that is higher than 50 crust, preferably between 50 and 80 crust.Can be with the C that obtains thus 3And C 4The LPG product separated mixes in the product of hydrocarbon and preparation from step (d).
The synthetic gas that in step (c), is used for Fischer-Tropsch reaction by the gas preparation that obtains in the step (a) by partial oxidation and/or steam/methane reformation.
In order to adjust the H in the synthetic gas 2/ CO ratio can be introduced carbonic acid gas and/or steam in the partial oxidation technology.The H of synthetic gas 2/ CO is than suitably between 1.3-2.3, preferably between 1.6-2.1.If desired, can prepare the hydrogen of (on a small quantity) additional content by steam methane reforming, the preferred combination water gas shift reaction.Also additional hydrogen can be used for other technology such as hydrocracking.
In another embodiment, the H of the synthetic gas that can will in the catalyzed oxidation step, obtain by from synthetic gas, removing hydrogen 2/ CO is than reducing.By accomplishing this point as routine techniquess such as transformation absorption or low temperature process.Preferential selection is a membrane separation technique.Hydrogen partial can be used for the especially hydrocracking step of Fischer-Tropsch reaction heavy hydrocarbon fraction.
Synthetic gas with above-mentioned this mode obtains has 900-1400 ℃ temperature usually, and it is cooled between 100-500 ℃, suitably between 150-450 ℃, preferably between 300-400 ℃, is preferably carrying out under generating electricity simultaneously with vapor form.Further be cooled to 40-130 ℃ with conventional heat exchanger especially tubular heater exchhanger, preferably between 50-100 ℃.Can use protection bed (guard bed) from synthetic gas, to remove any impurity.Especially can use special catalyst to remove all micro-HCN and/or NH 3Can may still be present in the Determination of Trace Sulfur in gases used in the step (c) by removing with the absorption technique of iron and/or zinc oxide.
The purge gas mixture that mainly comprises hydrogen, carbon monoxide and optional nitrogen contacts with suitable catalyzer in catalytic conversion stage, wherein forms the hydrocarbon that is generally liquid.
Those skilled in the art know the mixture through catalytic that is used in the step (d) comprising hydrogen and carbon monoxide and change into the catalyzer of hydrocarbon, and are referred to as Fischer-Tropsch catalyst usually.The catalyzer that is used for this method often comprises that the metal of periodic table of elements group VIII is as catalytic active component.Concrete catalytically-active metals comprises ruthenium, iron, cobalt and nickel.Consider to prepare heavy fischer-tropsch hydrocarbon, cobalt is preferred catalytically-active metals.As previously mentioned, preferred hydrocarbonaceous raw material is Sweet natural gas or accompanying gas.Because these raw materials produce H usually 2/ CO is than the synthetic gas that is approximately 2, and cobalt is extraordinary Fischer-Tropsch catalyst, because the use of this class catalyzer is 2 than approximately also.
Preferred supported catalyst reactive metal on porous support.Porous support can be selected from any suitable refractory metal oxide or silicate or their combination of knowing in this area.The object lesson of preferred porous support comprises silica, aluminum oxide, titanium dioxide, zirconium dioxide, cerium dioxide, gallium oxide (gallia) and their mixture, especially silica, aluminum oxide and titanium dioxide.
Catalytically-active metals amount on carrier is preferably the scope of every 100pbw solid support material 3-300pbw, and more preferably 10-80pbw especially is 20-60pbw.
If desired, catalyzer can comprise that also one or more metals or metal oxide are as promotor.The metal oxide promoter that is fit to can be selected from IIA, IIIB, IVB, VB and group vib or the actinide elements and the lanthanon of the periodic table of elements.Especially, the oxide compound of magnesium, calcium, strontium, barium, scandium, yttrium, lanthanum, cerium, titanium, zirconium, hafnium, thorium, uranium, vanadium, chromium and manganese is very suitable promotor.The particularly preferred metal oxide promoter that is used to prepare the catalyzer of the used wax of the present invention is manganese and Zirconium oxide.The metallic promoter agent that is fit to can be selected from the VIIB or the VIII family of the periodic table of elements.Rhenium and group VIII noble metals are particularly suitable, with platinum and palladium for preferred especially.The promotion dosage that is present in the catalyzer suitably is every 100pbw carrier 0.01-100pbw, preferred 0.1-40pbw, more preferably 1-20pbw.Most preferred promotor is selected from vanadium, manganese, rhenium, zirconium and platinum.
If catalytically-active metals and the promotor that exists can be by being deposited on the solid support material as any suitable processing of flooding, kneading and extruding.After metal and (if being fit to) promotor are deposited on the solid support material, usually load carriers is calcined.The effect of calcination processing is to remove the degradation production of crystal water, decomposing volatile and organic and mineral compound are converted into their oxide compounds separately.After calcining, can activate resulting catalyzer by catalyzer is contacted with hydrogen or hydrogen-containing gas, typically under about 200-350 ℃ temperature, carry out.Other method that is used to prepare Fischer-Tropsch catalyst comprise knead/grind, push, drying/calcining and activation.
Carry out catalytic conversion process under the conventional synthesis condition that can be known in the art.Typically, can be at temperature range 150-300 ℃, realize catalyzed conversion down for preferred 180-260 ℃.The typical total that is used for catalytic conversion process is a 1-200 crust (definitely), more preferably 10-70 crust (definitely).In catalytic conversion process, form the C that especially surpasses 75wt% 5+, preferably surpass the C of 85wt% 5+ hydrocarbon.According to catalyzer and conversion condition, pyroparaffine (C 20+) amount can be up to 60wt%, sometimes up to 70wt%, and sometimes even high to 85wt%.The preferred cobalt catalyst that uses uses low H 2/ CO is than (especially 1.7, or even lower) and use low temperature (190-240 ℃), optional and high pressure combination.Generate preferred at least 0.3 the H that uses for fear of any coke 2/ CO ratio.Especially preferably carry out Fischer-Tropsch reaction under certain condition, make the ASF-α value (the Anderson-Schulz-Flory chainpropagation factor) of the product that obtains be at least 0.925 with at least 20 carbon atoms, preferably at least 0.935, more preferably at least 0.945, even more preferably at least 0.955.Preferred fischer-tropsch hydrocarbon stream comprises 40wt%C at least 30+, preferred 50wt%, more preferably 55wt%, and C 60+/C 30+ weight ratio is at least 0.35, and is preferred 0.45, more preferably 0.55.
The preferred Fischer-Tropsch catalyst that uses, it can produce a large amount of paraffinic hydrocarbonss, more preferably not branched substantially paraffinic hydrocarbons.Being used for the only catalyzer of this purpose is to contain cobalt Fischer-Tropsch catalysts.Describe such catalyzer in the literature, as seen AU698392 and WO-A-9934917.
Fischer-Tropsch process can be slurries FT method or fixed bed FT method, especially multitube fixed bed.
Can directly isolate paraffin products by distilling in the product that obtains by step (d).In order to remove any alkene and the oxygenated compound of possibility negative impact, preferably at first make this cut fraction hydrogenation as the final blending properties of steam cracker feed stock.Also can isolate paraffin products from the effluent of hydrocracking step, described hydrocracking step carries out at all or part of of the product that obtains in the step (d).This paraffin products will comprise a large amount of isomerization alkanes.Isomerization alkanes and the ratio of n-paraffin are more preferably less than 0.3 preferably less than 0.5 in paraffin products.
Paraffin products preferably includes the C above 90wt% 5Extremely at 370 ℃ of following ebullient compounds.More preferably paraffin products seethes with excitement at naphtha range, preferably include above 90wt% from C 5Beginning is extremely at 204 ℃ of following ebullient compounds.
In step (e) with the C that obtains in paraffin products and the step (b) 3+ cut or C 5+ cut mixes.The product of step (d) with respect to the weight ratio of the product of step (b) preferably between 30: 1 to 5: 1.Resulting mixture preferably has following character:
Proportion is 0.65-0.74,
Plug baud colourity surpasses+20,
Unsaturated compound＜1 volume %,
Paraffinicity is 65%-100 volume %.
Isomery-normal paraffin compares less than 0.5,
Sulphur content is 50-650ppm, is preferably 100-650ppm,
Full boiling point be 150-204 ℃ and
Reed (Reid) vapour pressure in the time of 37.8 ℃ is no more than 13psi.
The invention still further relates to the mixture that obtains by method of the present invention and prepare the especially purposes of the third rare and/or ethene of light alkene as steam cracker feed stock.
Fig. 1 has illustrated method of the present invention.In material trap 1, isolate oil field condensation product 12 from sulfur-containing gas 11.In separator 2, oil field condensation product 12 is separated into low boiler cut 13 and high boiling fraction 14.Cut 14 is supplied with optional condensation product refinery.In Sa Fei nguktrum (Sulfinol) device 4, from the poor Sweet natural gas 15 that contains condensation product, remove desulfuration.In separator unit 5 with C 3+ hydrocarbon 17 is separated from the gas 16 of poor sulfur-bearing.By water distilling apparatus 6 hydrocarbon 17 further is divided into C 3With C 4Logistics 19 and mainly comprise C 5The logistics 18 of+hydrocarbon.
In synthesis gas preparation unit 7, utilize the gas 20 purified to obtain synthetic gas 21.This synthetic gas 21 as the raw material in the Fischer-Tropsch reaction step 8, is wherein obtained paraffin products 22.This product separation is become the cut of different boiling, comprise that boiling point is lower than the cut of naphtha fraction 24 (cut 23) and is higher than the cut (cut 25 and 26) of naphtha fraction.In mixed cell 10, naphtha fraction 24 is mixed with cut 13 and 18, obtain steam cracker feed stock 27 of the present invention.

Claims (14)

1. one kind is prepared the method for the steam cracker feed stock of sulfur-bearing by carrying out following steps by dirt gas:
(a) the liquid oil field condensation product cut of separate sulphur from Sweet natural gas,
(b) from Sweet natural gas, further separate the sour distillate that comprises hydrocarbon compound and obtain the process condensate thing with 3 or more a plurality of carbon atoms,
(c) prepare the mixture of carbon monoxide and hydrogen by the gas that obtains in the step (b),
(d) by utilization come from the carbon monoxide of step (c) and hydrogen carry out Fischer-Tropsch reaction prepare paraffin products and
(e) sour distillate that described paraffin products or the described product of part and comprising of obtaining is had the hydrocarbon compound of 3 or more a plurality of carbon atoms in (b) step mixes, and obtaining sulphur content is the sulfur-bearing steam cracker feed stock of 50-1000ppm.
2. according to the process of claim 1 wherein by gas cooling is carried out step (b) under the temperature and pressure condition of C3 and more higher hydrocarbon liquefaction.
3. according to the method for claim 2, wherein by cooling off with the liquid nitrogen indirect heat exchange.
4. according to the method for claim 3, wherein obtain liquid nitrogen when obtaining being used for the pure oxygen of step (c) preparation carbon monoxide and hydrogen mixture when separation of air.
5. according to the method for claim 2, wherein before the synthetic gas in utilizing gas preparation process (c), by reducing the C of pressure, separating and condensing 3+ hydrocarbon and optional rising stress level carry out step (b).
6. according to the method for claim 5, wherein in step (b), gas is reduced to the pressure that is lower than 40 crust from the pressure that surpasses 50 crust.
7. according to the method for claim 6, wherein pressure is reduced to and is lower than 30 crust.
8. according to each method among the claim 5-7,, gaseous tension is increased to the level of 50-80 crust wherein at the liquid hydrocarbon after separating.
9. according to each method of claim 1-8, wherein from the cut that comprises hydrocarbon compound, isolate C with 3 or more carbon atoms 3And C 4Hydrocarbon-fraction, and it is mixed wherein remaining C with the LPG product of product separation by preparation from step (d) 5+ hydrocarbon is used for step (e).
10. according to each method among the claim 1-9, wherein will be in step (a) isolating gaseous state oil field condensation product or the described gaseous state of part oil field condensation product mix with the product that in step (e), obtains.
11. according to each method among the claim 1-10, wherein in step (d), obtain and the paraffin products that in step (e), uses comprise surpass 90wt% from C 5Extremely at 204 ℃ of following ebullient compounds.
12. according to each method among the claim 1-11, wherein the sulphur content of the steam cracker feed stock that obtains in step (e) is greater than 50, and is preferred＞100ppm.
13. according to each method among the claim 1-12, wherein the steam cracker feed stock that obtains in step (e) has following character:
Proportion is 0.65-0.74,
Plug baud colourity surpasses+20,
Unsaturated compound＜1vol%,
Paraffinicity is 65%-100vol%,
Isomery-normal paraffin compares less than 0.5,
Sulphur content is 50-650ppm,
Full boiling point be 150-204 ℃ and
Reid Vapour Pressure under 37.8 ℃ is no more than 13psi.
14. the mixture that obtains by each method among the claim 1-13 prepares the purposes of the third rare and/or ethene as steam cracker feed stock.
CNB2004100104986A 2003-12-01 2004-12-01 Process to make a sulphur containing steam cracker feedstock Expired - Fee Related CN100430347C (en)

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CN100430347C CN100430347C (en) 2008-11-05

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CN110295054A (en) * 2018-03-22 2019-10-01 中国石油化工股份有限公司 A method of producing mixing isoparaffin

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Publication number Priority date Publication date Assignee Title
CN101410485B (en) * 2006-03-30 2013-06-19 国际壳牌研究有限公司 Process for the preparation of propylene and ethylene from a fischer-tropsch synthesis product
CN110295054A (en) * 2018-03-22 2019-10-01 中国石油化工股份有限公司 A method of producing mixing isoparaffin

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TW200528554A (en) 2005-09-01
JP2005171246A (en) 2005-06-30
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KR101176818B1 (en) 2012-08-27
SG112070A1 (en) 2005-06-29
CN1644652B (en) 2010-12-08
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CN100430347C (en) 2008-11-05
CN1644652A (en) 2005-07-27
KR20050053030A (en) 2005-06-07
TW200535230A (en) 2005-11-01

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