CN1310826C - Integrated process for making acetic acid and methanol - Google Patents
Integrated process for making acetic acid and methanol Download PDFInfo
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- CN1310826C CN1310826C CNB038116529A CN03811652A CN1310826C CN 1310826 C CN1310826 C CN 1310826C CN B038116529 A CNB038116529 A CN B038116529A CN 03811652 A CN03811652 A CN 03811652A CN 1310826 C CN1310826 C CN 1310826C
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- C01B3/025—Preparation or purification of gas mixtures for ammonia synthesis
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- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
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- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
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- C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
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- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
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- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/0838—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel
- C01B2203/0844—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel the non-combustive exothermic reaction being another reforming reaction as defined in groups C01B2203/02 - C01B2203/0294
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- C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
- C01B2203/82—Several process steps of C01B2203/02 - C01B2203/08 integrated into a single apparatus
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Abstract
The present invention provides a plant and a process that produces both methanol and acetic acid under substantially stoichiometric conditions, wherein an unadjusted syngas having an R ratio less than 2.0 is provided. All or part of the unadjusted syngas is supplied to a separator unit to recover CO2, CO and hydrogen. At least a portion of any one or combination of the recovered CO2 , CO and hydrogen is added to any remaining syngas not so treated or alternatively combines in the absence of any remaining unadjusted syngas to yield an adjusted syngas with an R ratio of 2.0 to 2.9 which is used to produce methanol. Any recovered CO2 not used to adjust the R ratio of the unadjusted syngas can be supplied to the reformer to enhance CO production. At least a portion of the recovered CO is reacted in the acetic acid reactor with at least a portion of the produced methanol to produce acetic acid or an acetic acid precursor by a conventional process.
Description
Technical field
Put it briefly, the present invention relates to from synthetic gas, make the method for acetate and methyl alcohol.
Background technology
Using carbonylating catalyst is known in the art from carbon monoxide and methyl alcohol manufacturing acetate.The representational reference of this method and similar approach is disclosed, the United States Patent (USP) 1 that comprises people such as Carlin, 961,736 (Tennessee Products), people's such as Paulik United States Patent (USP) 3,769,329 (Monsanto), people's such as Marston United States Patent (USP) 5,155,261 (Reilly Industries), people's such as Garland United States Patent (USP) 5,672,743 (BP Chemicals), people's such as Joensen United States Patent (USP) 5,728,871 (Haldor Topsoe), people's such as Denis United States Patent (USP) 5,773,642 (Acetex Chimie), people's such as Hinnenkamp United States Patent (USP) 5,817,869 (Quantum Chemical companies), people's such as Ditzel United States Patent (USP) 5,877,347 and 5,877,348 (BPChemicals), people's such as Denis United States Patent (USP) 5, people's such as 883,289 (Acetex Chimie) and Sunley United States Patent (USP) 5,883,295 (BP Chemicals), they are quoted as a reference separately in this article.
Be used for basic raw material that acetate makes yes carbon monoxide and methyl alcohol.In general acetic acid plant, input methyl alcohol, and carbon monoxide is because its transportation and store difficulty, so common by reformation Sweet natural gas or another kind of hydrocarbon and water vapour and/or carbonic acid gas generation in place.What in view of this, pay close attention to recently is the integration apparatus that structure is made methyl alcohol and acetate.The capital cost of new acetic acid plant is to generating the investment of the required equipment of carbon monoxide.What extremely need is that this investment can reduce significantly or at least significantly reduce.
In different places, the different time, market condition can cause lower methanol prices (surplus) and/or higher Gas Prices (shortage), can make production methyl alcohol profitless.The producer of existing methyl alcohol manufacturing facility can fall in the hope of profitable level in final bounce-back of product price and/or cost of material, faces the choice that whether continues to make methyl alcohol profitlessly.The present invention has also proposed a kind of method of improving existing nonprofit methanol plant, makes it in methanol prices can comparatively to get a profit when lower and/or Gas Prices is higher.
Following reference discloses the manufacturing of synthetic gas: Mayland (US 2,622,089), Moe (US3,859,230), people such as Steinberg (US 5,767,165), people such as people (US 5,855,815), Lee such as Park (US 5,180,570), McShea, (US 4 for people such as III, 927,857) and Banquy (US 4,888,130 and 4,999,133).It seems and confirm that for large capacity equipment, pure self-heating recapitalization may be the more economic method that generates synthetic gas, because can save huge investment by not building large-scale main reformer.In any case but shortcoming is fully to use all carbon molecules, thereby causes a large amount of CO
2Discharging, this is disadvantageous.Known to the applicant, there is not report to overregulate R ratio from the synthetic gas of the ATR that is used to make methyl alcohol, wherein R=[(H in the prior art
2-CO
2)/(CO+CO
2)], for example do not report yet, for making the MeOH and the CO of the metering of acetate providing chemical so that control methyl alcohol manufacturing and acetate manufacturing neatly, especially when the R ratio less than 2.0 the time.
Summary of the invention
An embodiment of the invention, relate to by the unregulated synthetic gas of at least a portion is separated into the air-flow that mainly is rich in carbon monoxide, hydrogen and carbonic acid gas, (1) optionally adds carbonic acid gas, carbon monoxide and/or the hydrogen from these air-flows in remaining unadjusted synthetic gas then, perhaps (2) are not having under the condition of remaining synthetic gas, merge these air-flows to make R ratio [R=(H
2-CO
2)/(CO+CO
2)] be the synthetic gas of the adjusting of 2.0-2.9, and use described synthetic gas to make methyl alcohol through regulating, then a part of methyl alcohol is reacted with approaching stoichiometric ratio with the described carbon monoxide air-flow of at least a portion and make acetate directly or indirectly, regulate the R ratio of the synthetic gas that is used for making methyl alcohol with this.
It is being equipment and the method for making methyl alcohol and acetate under the stoichiometric condition basically that embodiments of the present invention provide a kind of, and wherein the R ratio of unadjusted synthetic gas is less than 2.0.All or part of described unadjusted synthetic gas supplied to reclaim CO in the tripping device
2, CO and hydrogen.CO with at least a portion recovery
2, any or they in CO and the hydrogen in conjunction with adding in the remaining synthetic gas of handling like this, perhaps to produce the R ratio be that the synthetic gas through regulating of 2.0-2.9 is used for making methyl alcohol not having to merge under the condition of remaining unadjusted synthetic gas.Preferably, the R ratio of the synthetic gas of described adjusting is 2.00-2.05.Can the CO of recovery of the R ratio of described unadjusted synthetic gas will be used for regulating
2Supply to the output that increases CO in the reformer.The CO of the described recovery of at least a portion reacts with methyl alcohol that at least a portion makes in the acetic acidreaction device, makes acetate or acetate precursor by the method for routine.As mentioned above, the hydrogen of described recovery can be supplied to the MeOH synthesizer that is used for the methyl alcohol manufacturing.In the present invention, if the amount of the hydrogen that produces will surpass the synthetic amount that needs of methyl alcohol, described hydrogen also can be used to make ammonia or other product, the burning that acts as a fuel, perhaps output.Can use the excessive methanol of making aequum above acetate, for example, as making intermediate such as the methylamine that other product is used, perhaps as production marketing.
Excessive carbon dioxide can be sent in the reformer, Sweet natural gas and water vapour (water) charging in this reformer is used for making the synthetic gas of adjusting.Formed synthetic gas in this reformer, wherein, described Sweet natural gas is made the synthetic gas of comparing the carbon monoxide large percentage with the reformation that does not add carbonic acid gas with carbonic acid gas through reforming.
Separated hydrogen (if the amount of the hydrogen that produces surpasses the synthetic required amount of methyl alcohol in the inventive method) can also be reacted in the mode of routine with nitrogen and be made ammonia.In addition, the acetate of part generation can be with mode and the oxygen and the ethylene reaction formation vinyl acetate monomer of routine.Oxygen can be supplied to synthetic gas is provided in the autothermal reformer.The nitrogen that is used for the ammonia manufacturing processed can derive from conventional air separation plant with the oxygen that is used for vinyl acetate monomer process and/or autothermal reformer.
Put it briefly, on the one hand, the invention provides adjusting and be used for the methyl alcohol manufacturing separately or be used for the methyl alcohol manufacturing and the method for the R ratio of the bonded synthetic gas that acetate is made.This method is regulated the R ratio of unadjusted synthetic gas, is the unadjusted synthetic gas of at least a portion to be separated into be rich in CO
2, CO and hydrogen air-flow, in remaining unadjusted synthetic gas, add the CO of capacity then
2, CO and hydrogen air-flow in one or more, perhaps when not having remaining unadjusted synthetic gas, these air-flows of capacity are merged, make the synthetic gas that the R ratio is the adjusting of 2.0-2.9.
On the other hand, the methyl alcohol that at least a portion CO air-flow and at least a portion are made reacts in stoichiometric mode, makes acetate or acetate precursor by the method for routine.Based on consideration, can control the output of these two kinds of products to the economic aspect of acetate and methyl alcohol.For example, all methyl alcohol can be used to make acetate, perhaps can use the CO of more recovery to make methyl alcohol rather than make acetate, and the acetate that can make is just less like this, thereby causes the output of methyl alcohol to surpass the methyl alcohol of making the acetate aequum.Perhaps, can use the CO of recovery to make methyl alcohol, near the purposes perhaps its output being used for, thus cause not generating acetate.
In one embodiment, the present invention relates to jumbo methanol plants, wherein, synthetic gas is made by the self-heating catalytic reforming of Sweet natural gas and oxygen, and the carbon monoxide air-flow of q.s is invested manufacturing acetate; Remaining synthetic gas mixes with round-robin gas, and to send in the methyl alcohol synthesis cycle near stoichiometric ratio.
The method that the present invention proposes is eliminated above-mentioned background technical division and is divided mentioned shortcoming by with acetic acid plant and jumbo methanol plants combination.Synthetic gas is made by autothermal reformer, behind all feed materials of preheating, this synthetic gas of a part is sent into by CO
2In the tripping device that removal device and low temperature separation unit constitute, obtain the carbon monoxide air-flow, it is used in the acetate carbonylation equipment.All all circulate from the air-flow of described tripping device and the remainder of described unadjusted synthetic gas, make the synthetic gas of regulating, and this synthetic gas is sent in the methyl alcohol synthesis cycle subsequently.With the carbon monoxide air-flow from the synthetic gas capacity tell, the synthetic gas of make regulating is near the stoichiometric ratio of methyl alcohol manufacturing usefulness.This method has been removed from and has been built the required huge investment cost of main reformer.Another advantage is that methanol plant itself is " green " equipment, approaches zero because the release of carbon reduces to.
At first, the invention provides the method that a kind of manufacturing is used for producing the synthetic gas of methyl alcohol or carbinol derivatives, it may further comprise the steps: hydrocarbon, water vapour and oxygen are supplied in the autothermal reformer, produce the unadjusted synthetic gas that has hydrogen, carbon monoxide and carbonic acid gas at least, the mole R ratio of unadjusted synthetic gas is less than 2, and described R ratio is [H
2-CO
2]/[CO+CO
2]; The described unadjusted synthetic gas of at least a portion is separated into rich hydrogenous air-flow, is rich in the air-flow of carbon monoxide and is rich in the air-flow of carbonic acid gas; Preparing the R ratio by at least a portion that merges at least two strands of air-flows is the synthetic gas of the adjusting of 2.0-2.9, and these two strands of air-flows are selected from remaining unadjusted synthetic gas, the hydrogenous air-flow of described richness, the described air-flow of carbon monoxide, described air-flow and another carbon dioxide source that is rich in carbonic acid gas of being rich in; The synthetic gas input of described adjusting is used for making in the methyl alcohol synthesis cycle of methyl alcohol.
One preferred embodiment in, described method is further comprising the steps of: hydrogen-containing gas streams and the feed natural gas that contains higher hydrocarbon are merged, form hydrogenous feed stream; Described feed stream is contacted under hydrogenation temperature with a kind of hydrogenation catalyst, form the low pre-treatment air-flow of higher hydrocarbon content; Described pretreated air-flow is supplied in the autothermal reformer as described hydrocarbon.
Another preferred embodiment in, described method also comprises: by making methyl alcohol that at least a portion makes and the described air-flow that is rich in carbon monoxide of at least a portion with stoichiometric reaction, make the product of acetate or acetate precursor.
Another preferred embodiment in, described product comprises the precursor of acetate, the step that it is acetate that this method also comprises described acetate precursor conversion.
Another preferred embodiment in, the feed stream in the described contact procedure does not contain the water vapour of interpolation, is kept for hydrogenant low water content condition.
Another preferred embodiment in, described method also comprises: reclaim gaseous purge stream from described methyl alcohol synthesis cycle, and the described gaseous purge stream of at least a portion is recycled in the described contact procedure as hydrogen-containing gas streams.
Another preferred embodiment in, described method also comprises: recover hydrogen from described hydrogen gaseous purge stream; With described hydrogen recycle in described unadjusted synthesis gas flow.
Another preferred embodiment in, described method comprises that the hydrogen gaseous purge stream with described autothermal reformer front circulates.
Another preferred embodiment in, describedly also comprise: at least a portion is reacted with stoichiometric ratio basically from the air-flow that is rich in carbon monoxide of tripping device and at least a portion methanol stream from methanol synthesizer, form acetate, diacetyl oxide, methyl-formiate, methyl acetate or their bonded product.
Another preferred embodiment in, described product is acetate, diacetyl oxide, methyl-formiate, methyl acetate or their combination.
Another preferred embodiment in, described reformer is the autothermal reformer of operating under the temperature of pressure, 800-1250 ℃ at 20-80bar.
Another preferred embodiment in, the described air-flow that is rich in carbonic acid gas of at least a portion supplies in the described reformer, in order to improve the output of carbon monoxide.
Another preferred embodiment in, the R ratio of the synthetic gas of described adjusting is 2.00-2.05.
Another aspect of the present invention is to transform an original methanol plants, it has at least one and is used for hydrocarbon is converted into the steam reforming device of the synthesis gas flow that contains hydrogen, carbon monoxide and carbonic acid gas, and is used for hydrogen and the carbon monoxide methanol synthesizer that be converted into methyl alcohol of at least a portion in synthesis gas flow.This method is transformed into described original methanol plants and can makes methyl alcohol and make the equipment of a kind of product (described product is selected from acetate, diacetyl oxide, methyl-formiate, methyl acetate and their combination) by carbon monoxide and methyl alcohol, and the R ratio of the unadjusted synthetic gas that described equipment through transforming produces is less than 2.0.
The brand-new CO/MeOH equipment that compares, the advantage of described reforming equipment is to use conventional device and equipment, as desulfurizer, the reformer that comprises waste heat recovery, synthesic gas compressor and circulator etc.Owing to can use existing place and the equipment basis,, just can obtain additional advantage as water vapour producer, water treatment device, chilled water system, watch-keeping cubicle and product loading facility.
Reactions steps can comprise methyl alcohol and the carbon monoxide direct catalytic reaction in Monsanto-BP method for example, form acetate, perhaps also can comprise: the intermediate formation of formation methyl-formiate, methyl-formiate are to the hydrolysis of intermediate reaction, methyl acetate production acetate and the methyl alcohol of isomerization, CO and the two mole, of methanol generation methyl acetate of acetate or the carbonylation that methyl acetate generates diacetyl oxide.
Secondly, the invention provides a kind of original methanol plant is transform as produces methyl alcohol and contains acetate and the method for the equipment of the product of the acetate precursor that can be converted into acetate, it comprises: an original methanol plant is provided, and it has at least one and is used for convert hydrocarbons and forms and to contain hydrogen at least, the reformer of the unadjusted synthetic gas of carbon monoxide and carbonic acid gas, be used for cooling off the heat recovery equipment of described synthesis gas flow, compress the compression set of described synthesis gas flow, and be used for the methanol synthesizer that hydrogen and carbon monoxide with at least a portion in the described synthesis gas flow be converted into methyl alcohol; The described unadjusted synthetic gas from a reformer of at least a portion is turned to be entered in the synthetic gas tripping device; Operate described tripping device, the described synthetic gas that turns to is separated into the air-flow that is rich in carbonic acid gas, the air-flow that is rich in carbon monoxide and rich hydrogenous air-flow; The air-flow and the rich hydrogenous air-flow that make one or more air-flows that are rich in carbonic acid gas from described tripping device, are rich in carbon monoxide controllably are recycled in the described methanol synthesizer, make that the remaining unadjusted synthetic gas generation R ratio of bonded is the synthetic gas of the adjusting of 2.0-2.9 with it, wherein, described R ratio is [H
2-CO
2]/[CO+CO
2]; The acetic acidreaction device is installed, is made the air-flow that be rich in carbon monoxide and at least a portion methyl alcohol reaction from described methanol synthesizer, formation product of at least a portion from described tripping device.
One preferred embodiment in, described method also comprises transforms described reformer, thereby reduces the R ratio of described unadjusted synthetic gas.
Another preferred embodiment in, the R ratio of described unadjusted synthetic gas is less than 2.
Another preferred embodiment in, described reformer is an autothermal reformer, this method comprises that also air separation plant is installed generates the oxygen that is used for described autothermal reformer.
Another preferred embodiment in, described synthetic gas tripping device comprises solvent absorbing device and the desorption device that is used for carbon dioxide recovery, and the cryogenic distillation that is used for carbon monoxide and hydrogen recovery.
Another preferred embodiment in, described reformer is the steam reforming device, and an autothermal reformer is installed with it abreast.
Another preferred embodiment in, the R ratio of the synthetic gas of described adjusting is 2.00-2.05.
One of described remodeling method preferred embodiment in, the present invention also can transform an original methanol plants, and described original equipment has at least one to be used for hydrocarbon/water vapour feedstock conversion be steam reforming device, the heat recovery equipment that is used for the cooling syngas air-flow, the compression set that is used for the compressed synthesis gas air-flow that contains the synthesis gas flow of hydrogen and carbon monoxide and is used for hydrogen and the carbon monoxide compression set that be converted into methyl alcohol of at least a portion in synthesis gas flow.This can make a kind of product by carbon monoxide and methyl alcohol through the equipment of transforming, and described product is acetate, diacetyl oxide, methyl-formiate, methyl acetate and their combination.This remodeling method may further comprise the steps: (a) transform reformer and make it can make the R ratio less than 2.0 unadjusted synthetic gas; (b) at least a portion is turned to enters in the tripping device from the unadjusted synthetic gas of at least one steam reforming device; (c) described tripping device is installed, this device is separated into the air-flow that is rich in carbonic acid gas, the air-flow that is rich in carbon monoxide and rich hydrogenous air-flow with the described synthetic gas that turns to; (d) one or more air-flows that are rich in carbonic acid gas from described tripping device, the air-flow that is rich in carbon monoxide and rich hydrogenous air-flow controllably are recycled in the described methanol synthesizer, make that the remaining unadjusted synthetic gas generation R ratio of bonded is the synthetic gas of the adjusting of 2.0-2.9 with it; (e) the acetic acidreaction device is installed, this reactor can make at least a portion react the formation product with the methyl alcohol of at least a portion from described methanol synthesizer from the air-flow that is rich in carbon monoxide of described tripping device.
Described tripping device can comprise solvent absorbing device and the desorption device that is used for carbon dioxide recovery, and the cryogenic distillation that is used for carbon monoxide and hydrogen recovery.
This method can also comprise that the hydrogen and the nitrogen that make in the rich hydrogenous air-flow react the step of making ammonia.In the embodiment of reforming equipment, wherein, the rich hydrogenous air-flow of described original methanol plant produces, this air-flow comprises the loop purge from methanol synthesizer, make ammonia with nitrogen reaction, the equipment of described transformation can use excessive rich hydrogenous air-flow from described tripping device as the main sources of hydrogen of making ammonia.In some cases, with respect to original equipment, reforming equipment can be made additional ammonia.
Described method also comprises installs the vinyl acetate monomer device that is used for making a part of acetate and ethene and oxygen reaction manufacturing vinyl acetate monomer.Air separation plant can be installed to new or the equipment transformed in, be used for making and be used for the oxygen that vinyl acetate monomer manufacturing installation and autothermal reformer are used, and preferably, can satisfy the needs of manufacturing ammonia from the nitrogen of air separation plant.
Preferably, in the method, carbonic acid gas is about 0.1-0.5 with the mol ratio that comprises the hydrocarbon of Sweet natural gas in the reforming step charging, and the mol ratio of water vapour and Sweet natural gas is about 2-6.This method comprises that also the hydrogen and the nitrogen that make in the rich hydrogenous air-flow react the step of making ammonia in reactors for synthesis of ammonia.This method also can comprise becomes nitrogen gas stream and Oxygen Flow with air separation, and nitrogen gas stream is supplied to step in the reactors for synthesis of ammonia.When product comprises acetate and can be converted into the acetate precursor of acetate, this method also can comprise the Oxygen Flow from air separation plant, supplies to the step of making the vinyl acetate monomer air-flow in the vinyl-acetic ester synthesis reactor together with a part from the acetate and the ethene of carbon monoxide-methyl alcohol reactions steps.When autothermal reformer, this method also can comprise the oxygen from described air separation plant is supplied to step in the autothermal reformer.
Again on the one hand, the invention provides a kind of method of making the product of hydrogen and acetate, diacetyl oxide, methyl-formiate, methyl acetate and their combination, what this method was used is hydrocarbon (by intermediate methyl alcohol), carbon monoxide and carbonic acid gas, and surpasses the additional methyl alcohol of making described product aequum.This method comprises that (1) use the steam reforming hydrocarbon, forms to contain hydrogen, carbon monoxide and carbonic acid gas, and the R ratio is less than 2.0 unadjusted synthetic gas; (2) from described unadjusted synthetic gas, reclaim heat, form the unadjusted synthesis gas flow of refrigerative; (3) at least a portion is compressed to separating pressure through the unadjusted synthesis gas flow of refrigerative; (4) in tripping device, the unadjusted synthetic gas of described compression is separated into air-flow, rich hydrogenous air-flow that is rich in carbon monoxide and the air-flow that is rich in carbonic acid gas; (5) with remaining unadjusted synthetic gas, and the air-flow that is rich in carbon monoxide of capacity, rich hydrogenous air-flow and the air-flow that is rich in carbonic acid gas are sent in the methanol synthesizer, enter the carbonic acid gas that contains in the feeding gas of methanol synthesizer from another source, make that the R ratio of synthetic gas (being combined feed total feed) of the described adjusting of sending into methanol synthesizer is 2.0-2.9; (6) operation methanol synthesizer makes hydrogen in the synthetic gas of described adjusting and carbon monoxide and carbonic acid gas react with stoichiometry, obtains methanol stream; (7) at least a portion is reacted basically from be rich in carbon monoxide air-flow and at least a portion of described tripping device from the methanol stream of described methanol synthesizer with stoichiometric ratio, form acetate, diacetyl oxide, methyl-formiate, methyl acetate and their products such as combination.
No matter described equipment is reforming equipment or new installation, when product comprises acetate, preferably described reactions steps comprises: comprise carbon monoxide, water, a kind of solvent and comprise at least a halogenated promotor and condition that the reaction mixture of the catalysis system of the compound of at least a rhodium, iridium or their combination exists under, methyl alcohol, methyl-formiate or their combination are reacted.Preferably, the water-content of described reaction mixture is up to 20 weight %.When described reactions steps was simple carbonylation, the water-content in the described reaction mixture better was about 14-15 weight %.When described reactions steps was comprises low-water carbonylation, the water-content in the described reaction mixture better was about 2-8 weight %.When described reactions steps was the combination of methyl formate isomerisation or isomerization and carbonylation of methanol, the water-content in the described reaction mixture can be up to 2 weight % better greater than 0%.Preferably, this reactions steps is a successive.
Another embodiment of the invention provides a kind of method of pre-treatment feed stream, makes to use the ratio of water vapour and carbon lower, avoids simultaneously forming cigarette ash in the equipment of autothermal reformer and correlated process.In the method, the hydrogenous air-flow adding of richness is contained in the higher hydrocarbon feed stream of (containing 2 or a plurality of carbon atom), the mixture of gained is contacted under hydrogenation temperature with hydrogenation catalyst, and with the hydrogenant mixture together with forming synthetic gas in water vapour and the oxygen input autothermal reformer.Preferably, the hydrogenous air-flow of described richness is from sweep gas or its part of accepting synthetic gas or one partial methanol synthesis cycle.Preferably, so that the stoichiometric at least speed that higher hydrocarbon hydrogenation becomes the hydrogen of methane that is used for to be provided, the hydrogenous air-flow of described richness is added.Preferably, described hydrogenation temperature can be 300-550 ℃.Method equipment in this embodiment comprises: the feed gas feedway that comprises higher hydrocarbon; In have be used for transforming described higher hydrocarbon form the hydrogenation catalyst that the low air-flow of higher hydrocarbon content uses (generally as catalyzer be the base metal that is supported on aluminum oxide or the zeolite, as platinum, palladium, cobalt, molybdenum, nickel or tungsten) the pre-hydrogenation reactor; Be used for making low air-flow of higher hydrocarbon content and water vapour and oxygen reaction to form the autothermal reformer of synthesis gas flow; Be used for making from the hydrogen of described synthesis gas flow and the methyl alcohol synthesis cycle of reaction of carbon monoxide formation methyl alcohol; Gaseous purge stream from described methyl alcohol synthesis cycle; And be used for the described gaseous purge stream of a part is supplied to pipeline in the described pre-hydrogenation reactor.
Because this hydrogenation is heat release, described hydrogenation process can be finished in one or several reactor, optionally also has side cooler.This step of hydrogenation especially be fit to charging in the lower autothermal reformer of the ratio of water vapour and carbon together use.
Description of drawings
Fig. 1 (prior art) is to use the main-process stream block diagram of making the typical methyl alcohol/ammonia producing apparatus of ammonia from the hydrogen of methyl alcohol synthesis cycle sweeping gas, and it can be transformed for the purpose of making acetate according to the present invention.
Fig. 2 is that the equipment of Fig. 1 is being the improved main-process stream block diagram of purpose of manufacturing acetate, vinyl acetate monomer and additional ammonia according to the present invention.
Fig. 3 is the simplification schematic process flow diagram of the present invention's integration apparatus of making methyl alcohol and acetate.
Fig. 4 is the simplification schematic process flow diagram of integration apparatus of Fig. 3 that comprises the pre-hydrogenator of embodiment of the present invention.
Embodiment
Referring to Fig. 1, can be according to the original equipment of an embodiment of the invention transformation, have existing conventional steam reforming apparatus 10, methyl alcohol (MeOH) synthesizer 12 and preferably also have a synthetic ammonia installation 14, wherein, be used for the gaseous purge stream 16 of the hydrogen of described synthetic ammonia installation 14 from described methyl alcohol synthesis cycle.Remodeling method of the present invention can be widely used in any generation and uses synthetic gas to make the equipment of methyl alcohol.As employed in specification sheets and claims, " originally equipment " is meant the equipment of having built, is included in the transformation of the present invention middle structure of revising before.
Reformer means 10 generally is to have to have filled conventional reforming catalyst, as the roasting kiln of the parallel pipe of the nickel oxide of alumina-supported.The charging of reformer is the reformer feed of any routine, as lower hydrocarbon, and normally petroleum naphtha or Sweet natural gas.Reformer can be single-pass reformer or two-stage reformer, or any other commercially available reformer, and is for example well known to those skilled in the art available from Kellogg, Brown﹠amp; The KRES device of Root company.Originally the reformer effluent of methanol plants can contain the H of any routine
2: the CO ratio, but usually in the equipment of only making methyl alcohol near 2.0, and making isolating hydrogen product or intermediary hydrogen-containing gas streams, for example be used for the equipment of synthetic ammonia, can be high a lot, for example 3.0 or higher.Described hydrogen-containing gas streams is usually as obtaining from methanol synthesizer 12 round-robin gaseous purge stream 16, need prevent to cycle through the accumulation of hydrogen and rare gas element in the synthetic gas of described methanol synthesizer 12 with it.
According to the present invention, use reformer 10 and methanol synthesizer 12 and keep any synthetic ammonia installation 14, as shown in Figure 2, the original equipment (perhaps building new equipment) that comes transformation map 1 is in order to make acetate (HAC).The Oxygen Flow 66 of the air separation plant 50 of making a fresh start is in the future sent in the reformer 10, and in this embodiment, reformer 10 can comprise the autothermal reformer (ATR) parallel with existing steam reforming device or replace the ATR of described steam reforming device.A part is fed new CO by methanol synthesizer 12 through pipeline 20 from the effluent 18 of reformer 10
2In the removal device 22.For independent ATR, the R ratio of effluent 18 is less than 2, and for the combination of ATR and traditional steam reforming device, described R ratio is 2-3.Use conventional CO
2Separating device and method for example, absorb-desorb CO with solvent such as water, methyl alcohol, common hydrophilic alkanolamine such as thanomin, diethanolamine, methyldiethanolamine etc., hydrophilic alkaline carbonate such as yellow soda ash and salt of wormwood etc.
2Removal device 22 will become from the pneumatic separation of pipeline 20 and be rich in CO
2Air-flow and CO
2The air-flow 26 that content is low.This CO
2Absorption-stripping apparatus is buied with trade(brand)name Girbotol, Sulfinol, Rectisol, Purisol, Fluor, BASF (aMDEA) etc.The described CO that is rich in
2Air-flow can send in the charging of reformer 10 and/or by pipeline 24 and enter in the methyl alcohol synthesis cycle 12 by pipeline 60.
Can be with from CO
2The CO that reclaim in removal device 22 or another source
2Supply to the R ratio of regulating its charging in the methyl alcohol synthesis cycle 12.
Perhaps, can also be with CO
2Supply in the reformer 10 CO in reformer 10 chargings
2Increase increased CO content in the effluent 18.The steam reforming that forms synthetic gas with hydrocarbon and water vapour reaction is similar, and the reaction of hydrocarbon and carbonic acid gas often is called CO
2Reform.Along with the increase of carbon dioxide content in the reformer feed, by carbonic acid gas provide in product synthetic gas 18 in the carbon monoxide share of carbon increase with relative proportion, reduce from the share of the carbon of hydrocarbon.Therefore, produce speed, to the demand minimizing of hydrocarbon feeding gas for a given CO.At the commitment of reforming, heavy hydrocarbon is converted into methane:
Main water vapour and CO
2Reforming reaction is hydrogen and carbon monoxide with methane conversion:
Shift reaction is converted into carbonic acid gas and more hydrogen with carbon monoxide:
The conversion of heavy hydrocarbon is finished.Steam reforming, CO
2Reformation and shift reaction all are subjected to equilibrium-limited.Total reaction is a strong exothermic reaction.Optionally, can transform, be used to provide and replenish CO reformer 10
2Reform required additional heat and additional recovery of heat.
As mentioned above, from (the H of the effluent of reformer 10 that transform or self-heating
2-CO
2)/(CO+CO
2) mol ratio (in specification sheets and claims, be called " R ratio " (H
2-CO
2)/(CO+CO
2)) less than 2.As explaining hereinafter, can be by in remaining unadjusted synthetic gas, adding CO
2(through pipeline 60), CO (through pipeline 64) and/or hydrogen (through pipeline 62) are so that obtain having the synthetic gas 38 through regulating of required R ratio, and making it is optimum for methyl alcohol is synthetic, and preferably the R ratio is in the scope of 2.0-2.9.
CO
2The air-flow 26 that content is low mainly contains CO and hydrogen, it can be separated into the air-flow 30 that is rich in CO and 64 and rich hydrogenous air-flow 32 in CO tripping device 28.Tripping device 28 can be any equipment and/or method that is used for the CO/ hydrogen mixture is separated into purer CO air-flow and hydrogen stream, for example semi-permeable membranes, membranes, cryogenic fractionation etc.Low-temperature fractionation is preferred, can comprise and need not fractionated simple parts condense, condense with the part of fractional column, and optional can absorb (PSA) device and hydrogen recycle compressor, perhaps methane wash device with pressure-swing.Usually, with the part of fractional column the condense CO and the hydrogen of the enough purity that is enough to obtain to be respectively applied for the manufacturing of acetate and ammonia, and equipment and running cost are remained on minimum, but can add purity and the CO formation speed that PSA device and hydrogen recycle compressor increase hydrogen.For the acetate manufacturing, CO air-flow 30 preferable nitrogen and the methane that contain the hydrogen that is less than 1000ppm and be less than 2mol%.For the manufacturing of ammonia, send into the hydrogen stream 32 preferable 80mol% at least that contain of nitrogen wash unit (not shown), be more preferably the hydrogen of 95mol% at least.
A part of hydrogen stream 32 is supplied to replacement methanol loop purge stream 16 in the existing synthetic ammonia installation 14.The amount of the hydrogen that produces in the air-flow 32 is more much bigger than aforementioned amount through pipeline 16 supplies usually.This is because the methyl alcohol that makes in the reforming equipment is less to a great extent, so the synthetic used up hydrogen of methyl alcohol is less.This additional hydrogen capacity can be used as fuel, perhaps as being used for another process, for example increases the raw hydrogen source of ammonia transformation efficiency.The manufacturing of additional ammonia can be that the additional hydrogen of a part is supplied in the existing reactors for synthesis of ammonia 14 (transformation efficiency of ammonia increases in this reactor), and/or additional synthetic ammonia installation 33 is installed.The ammonia capacity that increases can seldom or without ammonia storage that change, existing and transportation equipment replenish by adapting to described additional ammonia capacity.
Methanol synthesizer 12 is a kind of methanol conversion device of routine, for example ICI reactor.Methanol synthesizer in the reforming equipment shown in Figure 2 with transform before basic identical in the original equipment, just the amount much less of the methyl alcohol of producing better is the only about half of of original equipment.Therefore, the recycle compressor (not shown) will be operated under lower capacity, and the amount of gaseous purge stream 16 also reduces significantly.As mentioned above, no longer need gaseous purge stream 16 to feed hydrogen gas in the ammonia convertor 14, because in the equipment of transforming, be to supply to the reforming equipment now from the hydrogen stream 32 of direct separation from the effluent 18 (this effluent is to transfer from the charging that enters methanol synthesizer 12 through pipeline 20) of a part of reformer 10.Optionally, can use gaseous purge stream 16 to act as a fuel and/or as the sources of hydrogen of hydrogenating desulfurization of the charging that is used for reformer 10.Since no longer need to make excessive hydrogen stream to cross methanol synthesizer 12 to be used in the ammonia device 14, as above-mentioned, can be in the charging of compositionally optimized methanol synthesizer 12, promptly effluent 18, so that more effectively carry out methanol conversion.Also may need to change methanol synthesizer 12 (optionally can in transformation process), make it comprise any other change that does not have in the original equipment, this is because the structure of original equipment is limit, and these are changed and have become conventional and begun to be used for the methyl alcohol synthesis cycle.
Preferably, balance redirect to CO from reformer 10
2/ CO/H
2The amount of the synthetic gas in the effluent 18 of tripping device is balance in addition, in order to methyl alcohol and the CO that stoichiometric ratio is provided, thereby makes acetate in acetate synthesizer 34.Preferably, the ratio of the methyl alcohol in CO in the pipeline 30 and the pipeline 36 about equally, perhaps many 10-20mol% of the amount of methyl alcohol, that is, mol ratio is 1.0 to about 1.2.For methyl alcohol and the CO that makes this ratio, the effluent 18 of relatively large (total kg/ hour) is turned in the intake pipeline 20, and its remaining small part sent into enter methanol synthesizer 12 in the pipeline 38.
Acetate synthesizer 34 uses acetic acid plant well known to those skilled in the art and methods, and equipment can also be the conventional equipment of buying, and for example, one or more in the patent of being made by above-mentioned relevant acetate as can be known.For example, can use conventional BP/Monsanto method, perhaps utilize the improved BP/Monsanto method of BP-Cativa technology (iridium catalyst), Celanese low water content technology (iridium-lithium acetate catalyst), Millenium low water content technology (rhodium-phosphorus oxide catalyst), Acetex technology (rhodium-iridium catalyst) and/or dual process carbonylation of methanol-methyl formate isomerisation.This reaction generally includes: comprise carbon monoxide, water, solvent and contain at least a halogenated promotor and condition that the reaction mixture of the catalysis system of the compound of at least a rhodium, iridium or their combination exists under, methyl alcohol, methyl-formiate or their combination are reacted.Preferably, the water-content of reaction mixture is up to 20 weight %.When described reaction was simple carbonylation, the water-content in the reaction mixture better was about 14-15 weight %.When described reaction was comprises low-water carbonylation, the water-content in the reaction mixture better was about 2-8 weight %.When described reaction is the combination of methyl formate isomerisation or isomerization and carbonylation of methanol, the water-content of described reaction mixture better greater than 0% until up to 2 weight %.This reactions steps is successive normally.Acetic acid product obtains by pipeline 40.
Optionally, a part can be sent in the conventional vinyl acetate monomer synthesizer 42 from the acetate of pipeline 40, in this synthesizer, acetate with from the ethene of pipeline 44 and at least a portion from the oxygen reaction of pipeline 46, obtain monomeric products air-flow 48.Can use for example conventional (better being cryogenic) air separation plant 50 to obtain the oxygen in the pipeline 46, this air separation plant also produce with pipeline 46 in the required corresponding nitrogen gas stream 52 of amount of oxygen (supply is used for the oxygen of vinyl acetate monomer synthesizer 42 and reformer 10) from the air of pipeline 54.Can make the amount of isolating air be suitable for making to be used for the required nitrogen that passes through pipeline 52 of the additional ammonia that adds by above-mentioned synthetic ammonia installation 33.
Referring again to Fig. 3, wherein show the equipment 100 of an embodiment that the present invention is used to make the synthetic method of acetate and methyl alcohol.Sweet natural gas 102 and air 104 are sent into a cogeneration system 110, be used for generating electricity 108 and produce water vapour 106.One or two produces oxygen the electrical energy fed that produces and air separation plant 112 (not shown) of nitrogen.Only there is the nitrogen of small part will be used for other device (instrument and safe liquid), unless the ammonia synthesis unit of having packed in the equipment 100.
The Sweet natural gas and the water vapour of Oxygen Flow and desulfurization are merged, and preheating in the preheater 114 of sufficiently high temperature (400-450 ℃), the catalyzed oxidation of charging in the initiation autothermal reformer 116.Described autothermal reformer 116 is in high pressure, high temperature (800-1250 ℃) operation down of 20-80bar.
The major advantage of this method is: (1) under high pressure obtains synthetic gas 118, comprises using a simple one-level or two-stage synthesic gas compressor (not shown); (2) high output temperature makes that the decrement (slip) (concentration of methane in the synthetic gas) of methane is very low.The R ratio of not regulating synthetic gas 118 is generally less than 2.
Use obtains high temperature by the heat exchanger (not shown) and comes preheated feed and/or produce water vapour.
The part 120 of refrigerative synthetic gas is sent into the CO that uses the thanomin operation
2In the removal device 122, produce the air-flow 130 that is rich in CO and be rich in H
2Air-flow 132.Tripping device 128 can be for example to have the part condensation cold box of two posts.
In this embodiment, air- flow 124 and 132 can mix with the other parts 134 of synthetic gas before entering methyl alcohol synthesis cycle 138, and producing the R ratio is 2.0-2.9, better was the synthetic gas 136 of about 2 adjusting.The synthetic gas 136 that the R ratio is about 2 adjusting produces the lower hydrogen gaseous purge stream 140 of flows.Preferably, the R ratio of the synthetic gas of described adjusting is 2.00-2.05.
Methyl alcohol synthesis cycle 138 is the low pressure synthesis cycle that produce methanol stream 146, and can produce water vapour.
Based on the consideration of economy, can use gaseous purge stream 140 to recover its calorific value, perhaps in film or PSA device 142, isolate gaseous purge stream 140 and come extract hydrogen 140 and be recycled in the main synthesis cycle 138.
The part 148 of the described methyl alcohol that makes is sent in the acetate synthesizer 150, carried out carbonylation, make acetate air-flow 152 with CO air-flow 130 from tripping device 128.154 of the other parts of methanol stream 146 are methanol product.
Referring to Fig. 4, the embodiment of method 200 is similar to Fig. 3, but comprises a pre-hydrogenator 202 and purge gas recycle 204.Pre-hydrogenator 202 is equipped with hydrogenation catalyst, for example, is generally used for the nickel-cobalt-molybdenum catalyzer of steam reforming, and it is for example operated down for 300-550 ℃ at suitable hydrogenation temperature.
Described sweeping gas circulation supplies to the hydrogenous air-flow of richness in the pre-hydrogenator, the higher hydrocarbon in the described feed stream is converted into lower hydrocarbon, for example methane.Hydrogen supply from circulating current should be enough to ground hydrogenation of the higher hydrocarbon stoichiometry in the feed natural gas or cracking are become lower hydrocarbon, better is methane.
Remaining sweeping gas can be sent into and reclaim all carbon molecules among the ATR.Will prevent inert compound in described methanol loop, as the accumulation of nitrogen or argon gas, because a part of synthetic gas enters the CO tripping device, and these inert compounds will be followed the CO air-flow usually.
Feed natural gas (better being mainly to be made up of methane) is in the desulfurization of the front of described pre-hydrogenator, and preferably the content of its water vapour is low.Preferably, described pre-hydrogenator, is operated under the condition that does not promptly have water vapour to supply with than low water content usually, it can with preheating in a usual manner, mix the usefulness that supplies preheating with the pre-hydrogenator effluent, different is can use higher preheating temperature because higher hydrocarbon content is lower.Many gas sources all contain not a spot of ethane, propane, butane and as United States Patent (USP) 6,375, can cause the C5+ hydrocarbon of formation cigarette ash in autothermal reformer 116 described in 916 as relevant gas.Pre-hydrogenator is converted into lower hydrocarbon with these higher hydrocarbons, that is, and and methane, and make reformer operation and do not form cigarette ash under the lower condition of water vapour and carbon ratio example.Use the inferior air-flow of sweeping gas described film/PSA device size or volume are reduced pro rata and/or elimination fully.Because hydrogen recycle is an internal recycling, material balance total in the equipment is constant basically.
Claims (20)
1. a manufacturing is used for producing the method for the synthetic gas of methyl alcohol or carbinol derivatives, and it may further comprise the steps:
Hydrocarbon, water vapour and oxygen are supplied in the autothermal reformer, produce the unadjusted synthetic gas that has hydrogen, carbon monoxide and carbonic acid gas at least, the mole R ratio of unadjusted synthetic gas is less than 2, and described R ratio is [H
2-CO
2]/[CO+CO
2];
The described unadjusted synthetic gas of at least a portion is separated into rich hydrogenous air-flow, is rich in the air-flow of carbon monoxide and is rich in the air-flow of carbonic acid gas;
Preparing the R ratio by at least a portion that merges at least two strands of air-flows is the synthetic gas of the adjusting of 2.0-2.9, and these two strands of air-flows are selected from remaining unadjusted synthetic gas, the hydrogenous air-flow of described richness, the described air-flow of carbon monoxide, described air-flow and another carbon dioxide source that is rich in carbonic acid gas of being rich in;
The synthetic gas input of described adjusting is used for making in the methyl alcohol synthesis cycle of methyl alcohol.
2. the method for claim 1 is characterized in that, it is further comprising the steps of:
Hydrogen-containing gas streams and the feed natural gas that contains higher hydrocarbon are merged, form hydrogenous feed stream;
Described feed stream is contacted under hydrogenation temperature with a kind of hydrogenation catalyst, form the low pre-treatment air-flow of higher hydrocarbon content;
Described pretreated air-flow is supplied in the autothermal reformer as described hydrocarbon.
3. the method for claim 1 is characterized in that, it also comprises:
By making methyl alcohol that at least a portion makes and the described air-flow that is rich in carbon monoxide of at least a portion, make the product of acetate or acetate precursor with stoichiometric reaction.
4. method as claimed in claim 3 is characterized in that described product comprises the precursor of acetate, the step that it is acetate that this method also comprises described acetate precursor conversion.
5. as each described method among the claim 2-4, it is characterized in that the feed stream in the described contact procedure does not contain the water vapour of interpolation, be kept for hydrogenant low water content condition.
6. method as claimed in claim 2 is characterized in that it also comprises: reclaim gaseous purge stream from described methyl alcohol synthesis cycle, and the described gaseous purge stream of at least a portion is recycled in the described contact procedure as hydrogen-containing gas streams.
7. method as claimed in claim 6 is characterized in that it also comprises:
Recover hydrogen from described hydrogen gaseous purge stream;
With described hydrogen recycle in described unadjusted synthesis gas flow.
8. method as claimed in claim 6 is characterized in that, it comprises that the hydrogen gaseous purge stream with described autothermal reformer front circulates.
9. as claim 1,2,3,4,6 or 8 described methods, it is characterized in that it also comprises:
At least a portion is reacted with stoichiometric ratio basically from the air-flow that is rich in carbon monoxide of tripping device and at least a portion methanol stream from methanol synthesizer, form acetate, diacetyl oxide, methyl-formiate, methyl acetate or their bonded product.
10. method as claimed in claim 9 is characterized in that, described product is acetate, diacetyl oxide, methyl-formiate, methyl acetate or their combination.
11., it is characterized in that described reformer is the autothermal reformer of operating under the temperature of pressure, 800-1250 ℃ at 20-80bar as claim 1,2,3,4,6 or 8 described methods.
12., it is characterized in that the described air-flow that is rich in carbonic acid gas of at least a portion supplies in the described reformer as claim 1,2,3,4,6 or 8 described methods, in order to improve the output of carbon monoxide.
13., it is characterized in that the R ratio of the synthetic gas of described adjusting is 2.00-2.05 as claim 1,2,3,4,6 or 8 described methods.
14. one kind transform original methanol plant as and produces methyl alcohol and contain acetate and can be converted into the method for equipment of product of the acetate precursor of acetate, it comprises:
An original methanol plant is provided, and it has at least one and is used for convert hydrocarbons and forms the compression set of the reformer of the unadjusted synthetic gas contain hydrogen, carbon monoxide and carbonic acid gas at least, the heat recovery equipment that is used for cooling off described synthesis gas flow, the described synthesis gas flow of compression and be used for the methanol synthesizer that hydrogen and carbon monoxide with at least a portion in the described synthesis gas flow be converted into methyl alcohol;
The described unadjusted synthetic gas from a reformer of at least a portion is turned to be entered in the synthetic gas tripping device;
Operate described tripping device, the described synthetic gas that turns to is separated into the air-flow that is rich in carbonic acid gas, the air-flow that is rich in carbon monoxide and rich hydrogenous air-flow;
The air-flow and the rich hydrogenous air-flow that make one or more air-flows that are rich in carbonic acid gas from described tripping device, are rich in carbon monoxide controllably are recycled in the described methanol synthesizer, make that the remaining unadjusted synthetic gas generation R ratio of bonded is the synthetic gas of the adjusting of 2.0-2.9 with it, wherein, described R ratio is [H
2-CO
2]/[CO+CO
2];
The acetic acidreaction device is installed, is made the air-flow that be rich in carbon monoxide and at least a portion methyl alcohol reaction from described methanol synthesizer, formation product of at least a portion from described tripping device.
15. method as claimed in claim 14 is characterized in that, it also comprises transforms described reformer, thereby reduces the R ratio of described unadjusted synthetic gas.
16., it is characterized in that the R ratio of described unadjusted synthetic gas is less than 2 as claim 14 or 15 described methods.
17. as claim 14 or 15 described methods, it is characterized in that described reformer is an autothermal reformer, this method comprises that also air separation plant is installed generates the oxygen that is used for described autothermal reformer.
18., it is characterized in that described synthetic gas tripping device comprises solvent absorbing device and the desorption device that is used for carbon dioxide recovery, and the cryogenic distillation that is used for carbon monoxide and hydrogen recovery as claim 14 or 15 described methods.
19., it is characterized in that described reformer is the steam reforming device as claim 14 or 15 described methods, and an autothermal reformer be installed with it abreast.
20., it is characterized in that the R ratio of the synthetic gas of described adjusting is 2.00-2.05 as claim 14 or 15 described methods.
Applications Claiming Priority (5)
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| US31925802P | 2002-05-20 | 2002-05-20 | |
| US60/319,258 | 2002-05-20 | ||
| US31991803P | 2003-01-30 | 2003-01-30 | |
| US60/319,918 | 2003-01-30 | ||
| PCT/CY2003/000002 WO2003097523A2 (en) | 2002-05-20 | 2003-05-20 | Integrated process for making acetic acid and methanol |
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|---|---|
| CN1656012A CN1656012A (en) | 2005-08-17 |
| CN1310826C true CN1310826C (en) | 2007-04-18 |
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| CN (1) | CN1310826C (en) |
| AU (1) | AU2003232578B2 (en) |
| EA (2) | EA007455B1 (en) |
| NO (1) | NO20045381L (en) |
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| AU2004229006B2 (en) * | 2004-11-08 | 2012-09-06 | Acetex (Cyprus) Limited | Autothermal reforming process for integrated production of acetic acid and methanol |
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| JP6161726B2 (en) * | 2012-12-21 | 2017-07-12 | ビーピー ケミカルズ リミテッドＢｐ Ｃｈｅｍｉｃａｌｓ Ｌｉｍｉｔｅｄ | Integrated process for making acetic acid |
| WO2014143840A2 (en) | 2013-03-15 | 2014-09-18 | Celanese International Corporation | Process for separating product gas using carbonylation processes |
| RU2747327C1 (en) * | 2017-06-28 | 2021-05-04 | Юниверсити Оф Саут Флорида | Systems and methods of production of liquid fuel from landfill gases |
| CN109574839B (en) * | 2017-09-29 | 2021-08-31 | 中国科学院大连化学物理研究所 | Method for directly producing methyl acetate and/or acetic acid by using synthesis gas |
| CN112262106A (en) * | 2018-06-08 | 2021-01-22 | 卡萨尔公司 | Methanol production method |
| CN111559949B (en) * | 2020-05-29 | 2022-12-02 | 中国海洋石油集团有限公司 | System and method for increasing yield of p-xylene by using carbon-rich natural gas |
| IT202200004013A1 (en) * | 2022-03-03 | 2023-09-03 | Milano Politecnico | Self-sustainable zero-emission process for the production of chemicals from organic sources |
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- 2003-05-20 EA EA200401498A patent/EA007455B1/en not_active IP Right Cessation
- 2003-05-20 EA EA200600482A patent/EA008283B1/en not_active IP Right Cessation
- 2003-05-20 WO PCT/CY2003/000002 patent/WO2003097523A2/en not_active Application Discontinuation
- 2003-05-20 CN CNB038116529A patent/CN1310826C/en not_active Expired - Fee Related
- 2003-05-20 AU AU2003232578A patent/AU2003232578B2/en not_active Ceased
- 2003-05-20 OA OA1200400302A patent/OA12861A/en unknown
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| US4464483A (en) * | 1981-06-12 | 1984-08-07 | Stamicarbon B.V. | Process for the preparation of methanol |
| US4522894A (en) * | 1982-09-30 | 1985-06-11 | Engelhard Corporation | Fuel cell electric power production |
| EP0233076A2 (en) * | 1986-02-10 | 1987-08-19 | Foster Wheeler Energy Limited | Process for the production of synthesis gas |
| EP0650950A1 (en) * | 1993-10-27 | 1995-05-03 | Mitsubishi Gas Chemical Company, Inc. | Process for the production of methanol |
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| EP1188712A2 (en) * | 2000-09-13 | 2002-03-20 | Toyota Jidosha Kabushiki Kaisha | Fuel reforming apparatus |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2003232578A1 (en) | 2003-12-02 |
| WO2003097523A2 (en) | 2003-11-27 |
| EA007455B1 (en) | 2006-10-27 |
| OA12861A (en) | 2006-09-15 |
| WO2003097523A3 (en) | 2004-04-29 |
| EA008283B1 (en) | 2007-04-27 |
| EA200401498A1 (en) | 2005-06-30 |
| CN1656012A (en) | 2005-08-17 |
| AU2003232578B2 (en) | 2009-03-12 |
| EA200600482A1 (en) | 2006-08-25 |
| NO20045381L (en) | 2004-12-09 |
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