CN1043493A - The method that from hydrocarbon raw material, prepares methyl alcohol - Google Patents

Abstract

A kind of method for preparing methyl alcohol by hydrocarbon raw material, this method comprises: at the raw material of the condition lower section catalysis hydro carbons of controlled temperature and steam so that obtain a kind of hydrogen that does not contain free carbon, the synthesis gas of carbon monoxide and carbonic acid gas, under the condition of preparation methyl alcohol, hydrogen, carbon monoxide and carbonic acid gas are reacted, then separation of methanol.

Description

The method that from hydrocarbon raw material, prepares methyl alcohol

The present invention is the relevant feedstock production methyl alcohol that uses hydro carbons (carbon compound class), this preparation process is to make the hydrocarbon raw material partial oxidation and produce the synthesis gas that contains hydrogen, carbon monoxide and carbonic acid gas, more further with this gas processing treatment and send into methanol synthesis loop.

Methyl alcohol all is to produce by the reaction of hydrogen and carbon monoxide and/or carbonic acid gas by following equation for a long time

Hydrocarbon raw material, for example the Sweet natural gas that comes near the exploitation oil oil field is exactly the raw material of suitable production methyl alcohol.Usually, the major ingredient of Sweet natural gas is methane and a spot of ethane, propane and butane.Sometimes when transforming, also contain lower boiling liquid hydrocarbon.

In order hydrocarbon feed to be transformed into be suitable for entering the feedstream of methanol sythesis reactor, at first need this raw material is transformed into the synthesis gas that contains hydrogen, carbon monoxide and carbonic acid gas.Adjust the ratio of hydrogen, carbon monoxide and carbonic acid gas by handling this synthesis gas, thereby obtain the suitable stoichiometric calculation ratio of methyl alcohol synthetic.Treated gas stream is compressed and sends into methanol synthesis loop, and carbon monoxide, carbonic acid gas and hydrogen react under the effect of catalyzer and generates methyl alcohol there, and methyl alcohol can use any routine techniques to be purified afterwards.

The method of having used in the methanol production process of prior art that hydrocarbon raw material is transformed into synthesis gas comprises steam reforming (reforming), the mixing steam conversion/and from thermal transition and partial oxidation.Steam reforming can be used the thermo-negative reaction equation of following methane and be represented:

Can use the thermopositive reaction equation of following methane represents:

The product of reaction equation (2) and (3) can according under establish an equation and change by heat release water gas shift reaction.

In steam reforming, the hydrocarbon raw material of desulfurization mixes with the vapor phase of two to four moles in the carbon of each mole and imports in the pipe that fills up catalyzer in the primary reformer, is transformed at this and mainly contains hydrogen, carbon monoxide, carbonic acid gas and the remaining methane and the synthesis gas of steam.Composition at the synthesis gas in converter exit is determined by the ratio of ingress's steam and raw material and the temperature and pressure of converter outlet.Use high steam-gas ratio and high temperature can increase output, but also increased the required fuel of converter simultaneously, and low voltage operatedly having improved required compression horsepower in the synthesis gas compressor, compressor can be sent to the synthesis gas of lower pressure in the higher methanol synthesis loop of pressure and go.The molar ratio that is typically steam and carbon (in the raw material) transformed organ pipe exit temperature at 850 ℃ to 888 ℃ at 2.8: 1 to 3.5: 1, and outlet pressure is at 15 to 25 crust.Under these working conditions, the about 3-4 mole of the content of residual methane (dry basis) in the synthesis gas.Waste heat in the thermal synthesis gas is used for improving vapor temperature and preboiler feedwater again.

The heat of thermo-negative reaction is to be provided by the burner near the dress autocatalysis agent pipe in the refractory-lined converter.Waste heat in the waste gas can be used to improve vapor temperature and superheated vapour, preheated burning air and is reclaimed.After recovery of heat and the last cooling, synthesis gas is compressed into the 50-100 crust in centrifugal compressor.

Fresh synthesis gas adds in the recycle gas of methanol synthesis loop at the suction port of loop compression device.In the discharge process of loop compression device, most recycle gas is preheating to 210 ℃ to 270 ℃ temperature of reaction and is admitted to the methanol sythesis reactor that catalyzer is housed.The methyl alcohol growing amount is lower under the synthesis reactor operational condition, generally has only 3.0-7.0%, depends on the working pressure of selection.This just causes needing a circulation loop system, and this system can make reactant repeatedly pass through catalyzer.

The gas that leaves reactor is used for preheating and enters the recycle gas of reactor, and thick then methyl alcohol is condensed in condenser and is separated in knockout drum.After the cleaning steam flow was removed, remaining gas turned back in the loop compression device, and inert methyl alcohol and excessive hydrogen are controlled in the synthesis loop whereby.Purging steam flow is utilized as converter fuel.Thick methyl alcohol is discharged in the light pressure separator by an outlet valve, at this dissolved gases flashing off and be sent in the converter fuel system.Thick methyl alcohol is purified in Distallation systm.

Habitual steam reforming technology is a kind of hydrogen-rich synthesis gas of the synthetic generation of methyl alcohol.The pressure that this excessive hydrogen must be compressed to the methyl alcohol loop is eliminated from the loop then as the fuel in the converter.

Steam reforming can replenish by a kind of stoichiometry synthesis gas that produces from thermal transition according to following reaction.

The desulphurised natural gas raw material is divided into two strands of steam flows.Import elementary (or once) steam converter after first strand of steam flow and the vapor mixing.Because excessive methane is oxidized in secondary (or secondary) convertor of back, compares with single primary reformer method, this primary reformer can be at higher pressure, lower temperature, and lower steam is to gas ratio work down.Synthesis gas from elementary steam converter mixes with second strand of gas material also and an importing of the oxygen of preheating secondary convertor.Reaction heat in the secondary convertor is provided by the burning of methane, hydrogen and carbon monoxide.Secondary convertor temperature out generally reaches 950 ℃ of waste heats in-1000 ℃ of thermal synthesis gases and is used for improving vapor temperature again, preboiler water inlet and distillation reboiler heat is provided.Waste heat from the waste gas of elementary steam converter is used to superheated vapour, preheating material and combustion air.With ordinary method relatively, the flow rate of the additional synthesis gas of reduction is under the higher pressure of ordinary method, therefore required compression power reduces greatly.The methyl alcohol building-up process is similar aforesaid method and the combining of steam reforming.

Owing to transform is to carry out in elementary and secondary convertor, and the size of primary reformer can reduce 75%.The carbon that contains in Fuel Demand minimizing and the raw material in the primary reformer more effectively utilizes the result who has reduced raw materials requirement, thereby makes the total amount (raw material: fuel) be lowered about 6% that Sweet natural gas uses.The result that primary reformer volume, volumetric flow of gas and compression power reduce, financial charges is also than using conventional method to reduce.

Require a large amount of relatively catalyzer from thermal conversion step.Generally, space velocity requires 8,000 and 12,000hr ^-1" space velocity " as used herein is that per hour numeral cited herein is meant pressure and temperature under the standard conditions by the volume of material of per volume of catalyst.

The partial oxidation of hydrocarbon raw material has represented to make at synthetic gas selectable a kind of method of steam reforming in the production.The partial oxidation technology that existing and methanol production is united use has been a kind of non-(nothing) catalyst process.Non-catalytic partial oxidation reaction effect is relatively low.Need carry out under higher temperature, promptly 3,200 °F to 2,800 °F (1205 ℃ to 1340 ℃) also need a large amount of oxygen.In addition, producing a large amount of free carbons also needs remove in next step.

Methanol process adopts partial oxidation, raw material to be compressed to about 30-80 crust in prior art, heats and imports in the partial oxidation producer.The oxygen of preheating is injected into the producer combustion chamber.According to reports, according to following reaction, raw material is transformed into rich carbon synthesis gas.

Heat for conversion reaction (2) and (8) thermo-negative reaction is supplied with by the methane of part reaction (7).This combustion reactions is the height heat release.The heat that synthesis gas had of leaving producer is greatly about 1400 ℃.These heats were used to improve vapor temperature before the carbon washer of this gas by a demonomerization carbon.

In order to adjust the ratio of carbon/hydrogen in the synthetic required synthesis gas of methyl alcohol, must basis reduce carbonoxide with making carbon monoxide be converted into carbonic acid gas such as following reaction,

Remove carbonic acid gas with any routine or the special-purpose sour gas method of removing then, perhaps directly remove carbon monoxide with pressurization revolution absorption (or claiming the absorption of pressure alternation).Additional heat utilize again and the adjustment of carbon/hydrogen ratio after, synthesis gas is compressed to synthesis loop pressure.Because this gas is stoichiometric and is in quite high pressure that the required energy of synthesis gas compression has just reduced.Yet the saving in the synthesis gas compression also needn't equal the saving of total expenses.The result of higher producer operating pressure increases the expense of oxygen compression and will comprise a Sweet natural gas compression device usually.This has a net increase of the requirement of energy, though concrete energy reduces, the compressor of running methyl methanol syngas body is energy requirement still.Compare with conventional steam reforming, in the needs of additional energy and the raw material carbonaceous poor efficiency utilization caused the especially increase of the demand of Sweet natural gas, that is: produce the Sweet natural gas that each unit methyl alcohol is consumed.

The transformation efficiency of oxidising process generally can improve by using catalyzer, but if oxidising process is a part, does not promptly have competent oxygen and be completely oxidized to hydrocarbon polymer, then will produce carbon precipitates and obstruction on the catalyzer.Carbon precipitates can be avoided with common uneconomic adding expensive catalysts.For example, United States Patent (USP) 4,087,259(is issued to Fujltani etc.), narrated the technology of using rhodium catalyst, in this method, the liquefied hydrocarbon raw material is vaporized, under 690 ℃ to 900 ℃ temperature, contact the rear section oxidation then, add volumetric flow rate simultaneously and be no more than (with the water of equivalent) additional steam of liquid hydrocarbon 0.5 as refrigerant with rhodium catalyst.Rhodium catalyst does not produce carbon deposition and makes and carry out partial oxidation, but is surpassing under 900 ℃ the temperature, and thermolysis then produces ethene or acetylene impurity.When adding steam, the amount of the hydrogen that is produced increases and decomposes owing to the steam catalytic decomposition becomes hydrogen and oxygen, and the output of carbon monoxide is constant.One per hour liquid space velocity (LHSV) from per hour 0.5 to per hour 25 open, be 20 particularly at 725 ℃ and CHSV, do not have under the steam situation and 800 ℃, CHSV is 2, has under the steam situation, obtains the high yield of gasoline vapor partial oxidation.

The service requirements of catalyzer is reflected in the specific space velocity scope and carries out in the partial oxidation technology.Use the catalyst member oxidizing process in the prior art,, must use and be lower than 12,000hr in order to obtain acceptable transformation efficiency ^-1Space velocity.As U.S. Patent number 4,522,894(authorizes Hwang etc.), the production of the hydrogen-rich gas of the battery fuel that acts as a fuel has been described.This technological process is the steam and the oxidant reaction of hydrocarbon polymer and input in an autothermal reformer that uses two catalytic domains.Per hour gross space speed is 1,960hr ^-1With 18,000hr ^-2Between.Because existing technological process must be carried out under low spatial speed, in order to obtain ideal output in industrial production, the part catalyst oxidation reactor of prior art must have big catalyst bed.This has just increased the size and the expense of partial oxidation reactor.

Production technique in order to provide one to produce methyl alcohol with hydrocarbon raw material is provided, this technology energy efficiency height, can uses inexpensive catalyzer, use less relatively, not expensive volume of equipment and obtain industrial acceptable output.

Further aim of the present invention is the production technique with hydrocarbon raw material production methyl alcohol that will increase the supply flow rate of hydro carbons with the oxygen of relatively low amount.

Above-mentioned and other purposes of the present invention can reach by following mode.

The invention provides a processing method of producing methyl alcohol with hydrocarbon raw material, compare with the existing methanol technics method of producing, it is the equipment that a kind of use is less relatively, expense is lower, with the method for higher relatively level of efficiency (relevant feedstock conversion).

The present invention provides a kind of processing method for producing methyl alcohol, resembles the part catalyzed oxidation of the hydrocarbon raw material of Sweet natural gas one class and a kind of oxidant stream and produce synthesis gas in this technological process, and in the reaction process, space velocity is 20,000hr ^-1To 500,000hr ^-1, temperature and steam condition do not produce free carbon basically, under the methanol production condition, and hydrogen, carbon monoxide and carbon dioxide reaction in the synthesis gas, and isolate (or claiming to reclaim) methyl alcohol.If necessary, the ratio of hydrogen, carbon monoxide and carbonic acid gas can be adjusted to reach the required suitable stoichiometry of reactant of methanol production reaction by removing carbon monoxide and/or carbonic acid gas in the synthesis gas.

In one embodiment, described the present invention comprises with the technology of hydrocarbon raw material production methyl alcohol:

(a) import a kind of hydrocarbon raw material to a part catalyzed oxidation district, the gaseous mixture of oxygen or oxygen-containing gas and selectable steam, wherein the molar ratio of steam and carbon is 0: 1 to 3.0: 1, the molar ratio of oxygen and carbon is 0.4: 1 to 0.8: 1, said mixed gas is being not less than 200 °F (93 ℃), but is lower than its spontaneous combustion, preferably is in or is higher than under its spontaneous ignition temperature and introduces part catalyzed oxidation district;

(b) with mixed gas by a kind of catalyzer that can make oxidizing hydrocarbon, make the hydrocarbon raw material partial oxidation a kind of mainly by the gas of methane, carbonoxide, hydrogen and vapor composition to generate in part catalyzed oxidation district, said catalyst surface area is at least 5cm with the ratio of volume ²/ cm ³And its volume can produce from 20,000hr ^-1To 500,000hr ^-1Space velocity;

(c) under the methyl alcohol formation condition, make hydrogen, carbonic acid gas and reaction of carbon monoxide, thereby generate a kind of product flow that contains methyl alcohol; And

(d) isolate this methyl alcohol

Description of drawings

Fig. 1 is the longitudinal sectional drawing of a catalytic partial oxidation reactor, and this reactor has a blender and a divider that is suitable for reagent is introduced catalyst bed in its input aperture.

Fig. 2 is the amplification longitudinal diagram that blender and divider break part among Fig. 1,

Fig. 3 is the vertical view that breaks part of blender and divider among Fig. 1.

Fig. 4 be among Fig. 1 blender and divider break the part fish-eye view.

Fig. 5 is Fig. 1 and the blender of Fig. 2 and the sectional view that feeder breaks part summary vertical planning drawing of expression critical size.

Fig. 6 is in the part catalytic oxidation, and oxygen and carbon molar ratio and steam and carbon molar ratio are for the curvilinear coordinates figure of three kinds of different operating temperature under this operating pressure of 400psig.

Fig. 7 is in part catalytic oxidation resultant, hydrogen and carbon monoxide molar ratio to steam and carbon molar ratio at 400psig(2760KPa) under this identical operating pressure, the coordinate diagram of three kinds of different working temperatures.

Fig. 8 be in part catalyzed oxidation product the shared percent volume of methane to steam and carbon molar ratio at 400psig(2760KPa) under this same operating pressure, the coordinate diagram of three kinds of different working temperatures.

Fig. 9 is that the shared percent volume of carbonic acid gas is compared at 400psig(2760KPa with the carbon molar ratio with steam in part catalyzed oxidation product) under this same operating pressure, the coordinate diagram of three kinds of different working temperatures.

Figure 10 be the molar ratio of total hydrogen and carbon monoxide in part catalyzed oxidation product to raw material in steam and carbon molar ratio at 400psig(2760KPa) the work coordinate diagram of three kinds of differing tempss under this same working conditions.

Figure 11 is a process flow sheet of producing methyl alcohol according to the present invention with hydrocarbon raw material.

Figure 12 is the sectional view that is used to produce the tube-cooled convertor of methyl alcohol according to the present invention.

Figure 13 is the process flow sheet of one first part of tame large-scale methanol production factory according to the present invention.

Figure 14 is the process flow sheet of large-scale methanol production factory of that family of Figure 13 second section.

Figure 15 is the process flow sheet of large-scale methanol production factory of that family of Figure 13 third part.

Figure 16 is one first part of tame small-sized methanol production factory process flow sheet according to the present invention.

Figure 17 is small-sized methanol production factory of that family of a Figure 16 second section process flow sheet.

The preferred embodiment explanation

Technology of the present invention mainly comprises following three steps: avoiding generating under the temperature and steam condition of free carbon, by the catalyzed oxidation of part, hydrocarbon raw material is being transformed into the synthesis gas of hydrogeneous, carbonic acid gas and carbon monoxide; Under the methanol production condition, make hydrogen, carbonic acid gas and reaction of carbon monoxide; Isolate methyl alcohol then.

Part catalyzed oxidation (also can claim catalytic partial oxidation)

Hydrocarbon class raw material part catalyzed oxidation according on August 14th, 1987 by M.Dunster and J.D.Korchnak application, and the common patent No. of transferring the possession of is that technology described in 085,160 the U.S. Patent application that awaits the reply is carried out.

An outstanding aspect of the present invention is exactly the saving of concrete financial charges and/or comes from the favourable process cost saving that the applying portion catalyzed oxidation produces material synthesis gas body required in the methanol production process.Owing to find the temperature when that a part of catalyzed oxidation that catalytic reaction zone outlet place measures carries out if the minimum temperature that equates or form greater than non-carbon, identical or greater than as the selected minimum temperature of linear function, this temperature comprises from 1600 °F (870 ℃) to 1900 °F (1040 ℃), the molar ratio scope of it and steam and carbon was at 0.4: 1 to 0: 1, the space velocity scope is 20,000hr ^-1To 500,000hr ^-1, on catalyzer, do not generate the free carbon precipitation thus, thereby make above-mentioned advantage become possibility.In addition, when oxidizing temperature is equal to or greater than minimum temperature, also find mainly to contain hydrogen, carbon monoxide and carbonic acid gas, need not add the formation that rhodium catalyst is prevented blocking at the product of part catalyzed oxidation of the present invention.As Fig. 6, total linear function of dotted line 25 expressions, when the ratio of steam/carbon is 0, least part oxidizing temperature corresponding to about 1900 (1040 ℃), when the ratio of steam/carbon is 0.4, corresponding to the least part oxidizing temperature of about 1600 (870 ℃), the suitable part catalyzed oxidation system that does not produce free carbon occurs in the point that is equal to or greater than on the line.In addition, can extrapolate by the linear function of line 25 expressions greater than 0.4 lower minimum temperature corresponding to the steam/carbon ratio.

Usually, the part catalyzed oxidation is the temperature that is measured with catalyst outlet, carries out in promptly from 1400 °F (760 ℃) to the scope of 2300 (1260 ℃).Be more preferably by the exit measured temperature, scope from 1600 °F (870 ℃) to 2000 °F (1090 ℃).Be lower than under 1400 (760 ℃) temperature, the methane of the not enough economic magnitude of unconverted is left, and when being higher than 2300 (1260 ℃) temperature, excess of oxygen is used.

The pressure that partial oxidation takes place is usually at 150psig(1030KPa) be preferably in 300psig(2060KPa).This pressure can surpass the pressure of methanol synthesis loop, and preferably pressure enters the required methyl methanol syngas body loop pressure of methanol synthesis loop above synthesis gas stream by processing unit.

Basically seldom or do not have conversion reaction to be used for technology of the present invention, that is to say that technology of the present invention only relies on partial oxidation and steam shift reaction (reaction equation 4) so that hydrocarbon raw material is transformed into synthesis gas basically.The part catalyzed oxidation of even premixed raw material and oxygen need not any conversion reaction and participates in.Catalyzer is selected to be used for promoting partial oxidation reaction and to need not any conversion reaction.Steam reforming reaction (reaction equation 3) generally needs a low spatial speed, promptly is about 12 usually, 000hr ^-1, and in the technology of using now used space velocity greater than 20,000hr ^-1Can prevent the effective steam reforming of raw material.It is believed that the production that increases hydrogen, be attributable to single partial oxidation, with steam reforming reaction (reaction equation 2) more should be owing to steam shift reaction (reaction equation 4).

Technology of the present invention can be used to hydrocarbon raw material is transformed into synthesis gas, has only the hydrocarbon of utmost point low levels to escape (unreacted raw material) if promptly hope has only 2% even lower.Because the reactivity in partial oxidation reactor is mass transfer limited, technology of the present invention can use more on a small quantity, more cheap catalystic material, if the ratio of catalyst surface area and volume conforms to requirement of the present invention.According to technology of the present invention, reactant gases is imported into reaction zone, i.e. reaction bed, and temperature in is not less than 200 °F (93 ℃) but is lower than the spontaneous ignition temperature of incoming mixture.The spontaneous ignition temperature of charging depends on the condition and the composition of incoming mixture and depends on used catalyzer.Preferably reactant gas imports to be equal to or higher than the mixture spontaneous ignition temperature.Another principal feature of part catalytic oxidation is that reactant is answered thorough mixing before reaction is carried out.Under proper temperature, import the reactant gases thoroughly mixed and can guarantee that the partial oxidation reaction mass transfer is controlled, therefore, reactivity is relatively irrelevant with catalyst activity, but relevant with the ratio (being specific surface area) of catalyst surface area and volume.Can adopt many materials as catalyzer, as long as it has required surface-area and volume ratio.Do not need to ask catalyzer that special catalytic activity is arranged to steam reforming reaction.According to the reaction conditions of regulation herein, if use as a kind of catalyzer, even be considered to not have the generation that the material of catalytic activity also can be used to promote synthesis gas usually with suitable configuration.Said herein " catalyzer " promptly trends towards comprising this class material.

The step of part catalyzed oxidation can be consulted accompanying drawing and be understood.Part catalyzed oxidation district specifically refers to the catalyst bed of reactor shown in Figure 1.As shown in Figure 1, the reactor that is used for the partial oxidation gas raw material comprises input and mixes and distribution portion, with 30 expressions.Mixing tank and divider 30 mix the inlet part that then mixture is assigned to the catalyticreactor of 32 expressions with oxygenant and raw material, are generated product and be sent to by partial oxidation at this raw material to be designated as 34 exit portion.

Reactor comprises a shell by structural metal such as carbon steel system, and it is not shown in the figures to be fixed with a top 42(with bolt or similar object on it), be the structural metal of carbon steel class.One thermal insulation layer 43 as the thermal insulation of 2300 (1260 ℃) BPCF ceramic fibers, is fixed on shell 40 upper inner at band top 42.In the lower section and output 34 of the mixing portion 30 in reactor part 32, matcoveredn 46,48 and 50 is fixed on the inside of shell.Protective layer 46 is a castable or similar insulation layer, as can anti-2000 (1090 ℃) ceramic thermal insulation bodies.Protective layer 48 also is castable or similar thermal insulator but contain 60% aluminium, with anti-3000 (1650 ℃) high temperature.Internal layer 50 is fire-resistant or similar thermal insulation layers, and for example 97% aluminium adds porcelain vase or 97% aluminium brick to resist reactor part internal medium.

Catalyticreactor part 32 comprises one or more catalysis (agent) dish 54.As shown in the figure, reactor comprises a series of catalysis (agent) dish, and each two-phase neighbour's dish by rich alumina ring 58 separately.The Pan Duo band is by the grid support of rich alumina bar 56.One thief hole 60 constitutes in the bottom of reactive moieties and a pipe 62 is arranged, and as the stainless steel tube of 309 types, prolongs the sample of removing product to return in firing tray 54 bottoms.

Output 34 suitably forms so that linked to each other by utilize boiler (not shown) or other processing units in downstream again.

Catalyzer is by the partial oxidation of a kind of high surface area material, energy catalysis hydrocarbon raw material.The configuration of this catalyzer can provide surface-area and volumetric ratio at least at 5cm ²/ cm ³Preferably the ratio of the geometrical surface of catalyzer and volume is at least at 20cm ²/ cm ³Yet the ratio to surface-area and volume does not have the strict upper limit, but is no more than 40cm usually ²/ cm ³The material of very multiple class can be used for constituting catalyzer, comprises the material that is considered to not have catalysis activity usually, as long as it has the ratio of ideal surface-area and volume.

For example catalysis dish 54 can be the one-piece construction with honeycomb type cross-sectional configuration.This suitable one-piece construction is littler than the employed size of the present invention technology, as the structural matrix of automobile exhausting catalytic conversion with as the catalytic combustor of the catalyzed oxidation of internal combustion turbine or water vapour.Particularly, one-piece construction comprises the horizontal pressure material of many conduits that extend along scantling length and constitutes honeycomb structure.These conduits generally are dimetric and can be piled into density up to cross section 1,200 per square inch.This one-piece construction can select for use any material to constitute, comprise trichroite (manganese oxide/aluminium sesquioxide/silicon oxide), manganese/magnesium oxide, trichroite (manganese, magnesium oxide/aluminium sesquioxide/silicon oxide), mullite (aluminium sesquioxide/silicon oxide), mullite aluminium titanate (muuite aluminium titanate) (aluminium sesquioxide/silicon-dioxide, aluminium sesquioxide, ferric oxide/silicon-dioxide) zirconium white spinel (Zirconia spinel) (zirconium dioxide/magnesium oxide/aluminium sesquioxide), spinel (magnesium oxide/aluminium sesquioxide), aluminium (aluminium sesquioxide) and Langaloy.One-piece construction can only contain a kind of these structured materials, though these materials itself are considered to not have catalytic activity.Use honeycomb structure, the ratio of surface-area and volume can meet or exceed 40cm ²/ cm ³Also can be on one-piece construction the activated oxide catalyst of coating tool, metal or metal oxide as is known.They comprise, as palladium, platinum, rhodium, iridium, osmium, ruthenium, nickel, chromium, cobalt, cerium, lanthanum and their mixture, other metals that can be used for applying catalysis dish 54 comprise I A, II A, III, IV, V B, VI B or the VII B family metal in the precious metal and the periodic table of elements.

Catalysis dish 54 also can be made of structural filler material, as is used to seal the stopping composition of adsorption tower.These packing materials are usually by very thin corrugated sheet metal, and are together tightly packed, form the siphunculus that runs through elongation.This packing material can be by the corrugated metal sheet, as superalloy stainless steel, chromium, manganese, molybdenum and refractory materials.If wish, these materials have the metal or the coating of metal oxides of catalytic activity with known to oxidizing reaction, as palladium, platinum, rhodium, iridium, osmium, ruthenium, nickel, chromium, cobalt, cerium, lanthanum and their mixture.

Catalysis dish 54 also can be made of the wire cloth of densification, as superalloy or platinum gauze.If wish, wire cloth is also available to have active metal of oxidation reaction catalysis or coating of metal oxides, comprises palladium, platinum, rhodium, iridium, osmium, ruthenium, nickel, chromium, cobalt, cerium, lanthanum and their mixture.

The surface-area of any above-mentioned catalyst configuration and the ratio of volume can use following method to be increased, be about to contain on weight about 1% or granular metal still less or metal oxide, as lead, or I A, II A, III, IV, V B, metal water rare (silt) the slurry coating of VI B and VII B family, and at high temperature the roasting coatingsurface makes granular metal stick to the surface, but temperature is too not high, in order to avoid make surperficial sintering.Used particle requirement BGT(Brunnauer-Emmett-Teller) (mensuration surface-area) surface-area is greater than 10m ²About/gram, more preferably greater than about 200m ²/ gram.

Hydrocarbon raw material, oxygen or a kind of oxygen-containing gas, as air, the gaseous mixture that perhaps also can comprise steam is introduced part catalyzed oxidation district in the temperature that is not less than 200 (930 ℃) but be lower than under its spontaneous ignition temperature.Preferably gaseous mixture is being equal to or greater than the catalytic oxidation zone of entering part under its spontaneous ignition temperature.In reaction zone, because the heat of reaction will provide the temperature of charge necessary energy that raises, thereby can allow reactant enter reaction zone being lower than under its spontaneous ignition temperature, with mass transfer master mode control response device.In this case, usually need be to reaction zone inlet input heat, as by a spark 7 devices or will comprise that before reactant is imported material is preheated to above its spontaneous ignition temperature with initiation reaction in the reactor of catalyzer.Surpass 200 °F (93 ℃) if the temperature of the reactant of reaction zone inlet is lower than the value of spontaneous ignition temperature, it is unstable that reaction just becomes.

When reaction mixture to surpass its spontaneous ignition temperature entering part catalyzed oxidation district, just mixture should be imported catalytic bed once mixing, promptly before spontaneous combustion disappearance time of lag, the mixture of hydrocarbon class raw material and oxygenant preferably should be introduced catalytic bed.It also is very important that gas reactant must thoroughly be mixed.Reactant undercompounding will reduce the quality of product and cause overheated.With hydrocarbon class raw material and oxygen or oxygen-containing gas mixing and distribution, be shown in Fig. 1-5 with the reactant importing reaction zone appropriate device that guarantees thorough mixing and will it heating in the shortest time, and be that more detailed description has been done in the patent application of awaiting the reply of U.S. of 085,159 in application on August 14th, 1987 and the common series number of transferring the possession of by J.D.Korchnak M.Dunster and J.H.Marten.

Referring to Fig. 1, one of air feed, that is hydrocarbon gas or oxygen-containing gas through first input channel 66, pass top 42, enter inlet part 30, and top 42 communicate with last charging conical hopper (cone) 68.Conical hopper 68 is fixed on top 42 by supporting 69.Other feed gas import importations 30 by second import 70, the stretch side channels of housing 40 of import 70, and link to each other with second Room 72, second Room 72 is to be inserted between the import of upper chambers 68 and catalyst reaction part 32.

Have a ring 73 to be positioned at upper wall 75 centres of chamber 72, with the following involution of funnel 68, so wall 82 has formed a common wall between last chamber 68 and following chamber 72.There is the also visible Fig. 2 and 3 of a top outer ring portion 74(chamber 72), it is to be supported by the upper surface of fire-resistant (material) layer 50.There is a tubular wall 76 chamber 72, and it stretches fire-resistant (material) sleeve 50 down downwards, and the bottom of wall 76 is made of foundry goods 78.

Optionally steam is imported in hydrocarbon raw material and oxygen or the oxygen-containing gas.Gas is admitted to reactor with corresponding ratio, and the molar ratio of its steam and carbon is from 0: 1 to 3.0: 1, preferably from 0.8: 1 to 2.0: 1.The ratio of oxygen and carbon is from 0.4: 1 to 0.8: 1, and preferably from 0.45 to 0.65.Though air can be used as oxygenant in technology of the present invention, but use oxygen or oxygen rich gas are better, also in order to reduce inert fraction as far as possible, as this composition that must bring in the system of nitrogen." oxygen enrichment " be meant and contain 70 moles of % oxygen at least, preferably at least 80 moles of % oxygen.

Reaction-ure mixture is preferably with spontaneous combustion or be higher than under the temperature of spontaneous combustion and enter catalyticreactor part 32.According to concrete reactant gases ratio, reactor operating pressure and employed catalyzer, temperature be generally 550 °F (290 ℃) and, 1,1000 °F (590 ℃).Be preferably in by entering the mouth before 70 or 66, hydrocarbon raw material and steam are mixed and be preheating to 650 °F (340 ℃) to 1,200 °F (650 ℃).Oxygen or oxygen-containing gas as air, are heated to 1200 °F (650 ℃) then by other inlets 66 or 70 from 150 °F (65 ℃).

Again referring to Fig. 1, to mix and distribution device is that pipe 80 by many elongations carries out, the top of these pipes is fixed on the upper wall 75 of chamber 70.Chamber at the pipe of upper end links to each other with last chamber 68.The bottom of pipe 80 and parts 78 link closely, and the chamber of pipe links to each other with passage 84 upper ends, and passage 84 is vertical by parts 78.Aperture 86 forms on the wall of pipe 80, is used in the chamber from the air-flow of chamber 72 guiding pipe 80.Import 66 and 70, funnel 68, bearing 69 is made by common corrosion-resistant and heating resisting metal, and chamber 72 pipes 80 and parts 78 are to be made by common superalloy or fire safe type material.

The quantity of pipe 80, the internal diameter 90(of pipe 80 sees Fig. 5), the size of aperture 86 and quantity are according to selecting by the flow velocity and the pressure of 66 and 70 the gas of entering the mouth in every pipe, so that manage turbulization in 80, velocity in pipes surpasses back flash (flashback) speed of mixture.Form divergence passage 84 ingress leading to open, the minor increment 92 that aperture 86 leaves pipe 80 bottoms is through selecting to be equal to or greater than under turbulence state the needed distance of air-flow thorough mixing from chamber 68 and 72.The size of pipe 80 internal diameter 90 and the length 94 of pipe be specialized designs the enough pressure of generations falls the reaction chamber process to lead to from chamber 68 at gas, form from the chamber 68 thus and lead to and manage 80 basic uniform airflow.Equally, the size of aperture 86 is also selected, for the speed and pressure that enter import 70 with respect to gas, in chamber 72 with manage and provide enough pressure to fall between 80 inside, provides the basic gas stream uniformly that enters pipe 80 through small holes 86 thus.

Divergence access structure in parts 78 in order to the flow velocity that reduces gas so that to catalyst inlet uniformly distributing gas.Path 84 cross section increment rates are to descend and increase along with its, angle 98, i.e. and the angle of the wall of path 84 and the straight wall of pipe 80 is generally equal to or less than 15 °, preferably angle is equal to or less than 7 °, to reduce or to avoid producing eddy current for 84 li at path as far as possible.This guaranteed near or surpass under the spontaneous ignition temperature, blended gas preferably enters catalytic bed to be shorter than the time that spontaneous combustion postpones fully basically.

The gas that comes from the part catalyst oxidation reactor contains hydrogen, carbonic acid gas, carbon monoxide and a part of methane.The synthesis gas that leaves catalytic domain is at first cooled off by heat exchanger, both available heated hydrocarbon and delivery of steam raw material also can flow by heated oxidant, pass through superheated vapour, or in boiler, improve vapor temperature, by preboiler feedwater or above-mentioned any combining method.

The adjusting of hydrogen and oxycarbide ratio

The gas stream that is converted into methyl alcohol in methanol synthesis loop comprises hydrogen and oxycarbide (or claiming carbonoxide), i.e. carbonic acid gas and carbon monoxide.In the gas that will transform, the mol ratio of hydrogen and oxycarbide can be expressed as methyl alcohol stoichiometry synthesis gas than (MSSGR), and this MSSGR is defined by following mol ratio:

MSSGR = (H ₂)/(2CO + 3CO ₂)

This MSSGR value is at least 0.8 concerning methyl alcohol is synthetic, is preferably 0.95 to 1.1.Normally, the synthetic gas circuit that obtains from the part catalyst oxidation reactor is rich carbon, that is, this MSSGR is lower than the theoretical expectation value slightly.In order to proofread and correct this stoichiometry, should or from the sweep gas that the methanol synthesis loop ring, obtains, remove carbon from the synthesis gas that leads to methanol synthesis loop, methyl alcohol loop.

Carbonic acid gas can remove from synthetic air by any known method.For example, this gas stream can be by the adverse current liquid flow of a carbonic acid gas adsorption medium.The treatment unit that removes carbonic acid gas can obtain on market, and for example, trade mark is house Rec Xi Er (Selexol), amanil Ka Te (Amine Gaard) and this Felder (Benfield) etc.

Because the content of the carbonic acid gas in synthetic gas is lower, it also is necessary removing the part carbon monoxide, to obtain ideal MSSGR.The method of any known removal of carbon monoxide all can be used.A kind of suitable method comprises that transforming at least a portion carbon monoxide by gas shift reaction is carbonic acid gas, removes carbonic acid gas then from air-flow.This gas shift reaction is known, and realizes that the suitable device of this reaction is available on the market.

The method that another kind removes carbon oxides is pressure alternation absorption method (pressure swing absorption).This method not only can be applied to the desired amt of removal of carbon monoxide and/or carbonic acid gas, can also be applied to remove to the unwanted air-flow component of preparation methyl alcohol, for example methane and nitrogen.Pressure alternation absorption method comprises the component that absorption is under high pressure desired to be removed, desorb under low pressure then.This method has two basic steps: operated in absorption and the regenerated recirculation.Because some hydrogen that in waste gas, lose in the regeneration stage, thereby be not that all hydrogen can both reclaim, but by careful frequency and the order of selecting step in the circulation, it is maximum that the recovery of hydrogen can reach.

The regeneration of sorbent material can be achieved by three basic steps:

(a) sorbent material is reduced to low pressure.Some useless components are able to desorb in this step.

(b) sorbent material purges with hydrogen gas product under base pressure, removes the useless component of retention.

(c) sorbent material is forced into adsorptive pressure again with standby.

Pressure alternation absorption method is applied to remove carbon oxides and inert substance most effectively, for example, and methane in the methanol synthesis loop and nitrogen.

Synthesizing of methyl alcohol

Hydrogen, carbonic acid gas and carbon monoxide react under the formation condition of methyl alcohol.Any known method with hydrogen, carbonic acid gas and reaction of carbon monoxide generation methyl alcohol can be used.Preferably, they at about 50 normal atmosphere (5070 kPas) under 120 normal atmosphere (12160 kPas), in a circulation catalyticreactor, under middle-pressure process, react, be to 100 normal atmosphere (10130 kPas) better from about 70 normal atmosphere (7090 kPas).This class synthesis method and its device of realization are known technology.

This synthetic gas is compressed between 50 normal atmosphere (5070 kPas) and 120 normal atmosphere (12160 kPas), is preferably between 70 normal atmosphere (7090 kPas) and 100 normal atmosphere (10130 kPas).This gas enters a methyl alcohol synthesising container and mixes with recycle gas in this container.This gas enters a methyl alcohol catalytic converter subsequently.This methanol converter generally comprises a pressurized vessel, and this pressurized vessel comprises that a catalyst bed is convenient to relax the facility that hydrogen and carbon oxides generate the thermopositive reaction of methyl alcohol, for example, injects freezing air by compartment of terrain in catalytic bed.

Any available on the market, can catalysis hydrogen, carbonic acid gas and carbon monoxide can use with the catalyzer that generates methyl alcohol.These catalyzer are made by for example Imperial Chemical Industries (Imperial CHemical Industries), cartel material (Katalco) and (Haldor Topsoe) company of Soviet Union of Hao Erde Top.Preferable methanol synthesis catalyst is made up of zinc oxide and cupric oxide.This methyl alcohol building-up reactions generally occurs in about 410 Fahrenheit degrees (210 degrees centigrade) in the temperature range of 570 Fahrenheit degrees (300 degrees centigrade), depends on the activity of employed specific catalyst.

Expellant gas passes through one by water-cooled condenser from methanol converter, feeds a separator then, and the bottoms of separator comprises the methanol condensed thing.A certain amount of gas purges from methanol synthesis loop and removes, thereby in circulation the concentration of rare gas element is maintained acceptable level.The gas of retaining is being admixed and is being remained recirculation and advance the input synthetic gas of methanol converter.

As previously pointed out, carbon monoxide and/or carbonic acid gas both can remove from the circulation gas of methanol synthesis loop, also can remove from sweep gas to keep desirable MSSGR, preferably 0.96 and 1.10 allow and enter convertor.When carbon oxides removes from sweep gas, the hydrogen-rich gas of retention makes and is recycled in the methanol synthesis loop.

Aqueous thick methyl alcohol is just purified to obtain refining pure methyl alcohol by traditional method.Preferably, methanol condensed thing purifying in one or more distillation tower.

Method of the present invention can be understood further with reference to the schema of Figure 11.

Compare with current commercial run, the part catalytic oxidation provides following advantage.

(1) saved the steam converter of high cost.

(2) catalyst volume is less than the steam conversion or from the used catalyzer of thermal transition.

(3) oxygen consumption is lower than traditional no catalytic partial oxidation process.

(4) water consumption is lower than that steam transforms or steam transforms and adds from thermal transition.Therefore this method be particularly suitable for water be difficult to obtain (for example in waste original area) or very expensive in (for example needing make) through desalination.

(5) compare with the method that steam is converted into methyl alcohol, the requirement of geographic coverage has been reduced (being particularly suitable for the utilization in coastal waters).

(6) with regard to feedstock conversion, efficient is higher than existing method (no matter being to transform or partial oxidation).

(7) investment cost is lower than the method on all existing markets.

The process flow sheet of methanol device that is designed to maximum efficiency is shown in Figure 13-15.Hydrocarbon raw material, for example natural gas flow 200 among Figure 14 is optionally to remove sulphur with traditional method.For example, sulphur removal can be passed through the hydrocarbon-containifirst raw material preheating traditionally to the temperature between about 250 Fahrenheit degrees (120 degrees centigrade) and 750 Fahrenheit degrees (400 degrees centigrade), and sulfide is adsorbed onto on the zinc oxide that is included in one or several desulfurization container 202.This desulfurization container 202 is arranged on the upstream of the hydrocarbon-containing feedstock saturex 204 of embodiment as shown in figure 14; In addition, desulfurization container 202 can be arranged on the downstream of synthetic gas compressor, shown in the embodiment of Figure 16.

Hydrocarbon raw material after the desulfurization in forcing film saturex 204 by steam-laden.This pressure film saturex 204 are one of these method with from different features, compare with the saturex than prior packed tower of present industrial application, its investment cost and energy requirement are all lower.This pressure film saturex 204 includes a upright shell and the tubular exchanger and a recycle system 206.Desulfurization hydrocarbon raw material and water enter the top 208 of interchanger and inflow pipe 210 vertically downward.This raw material is heated when flowing through this pipe, for example arrives a temperature that is approximately 400 Fahrenheit degrees (206 degrees centigrade), and when it heated, the content of water vapour was owing to the vaporization of recirculated water increases.Heating medium is the discharge air-flow 330 of methanol reactor in this case, flows by the shell-side of pipe 210 and the direction opposite with feedstream in the bottom of forcing the film saturex, discharges in exit, housing top with lower temperature.The water of this desulfurization hydrocarbon raw material and not vaporization appears at the bottom and 212 separates in the bottom from exchanger tube 210.Isolating water is recycled to the top 208 of forcing the film saturex by pump 206, and saturated then hydrocarbon raw material leads to saturated raw material pipeline 220.Supplementary feed 216 joins in the recirculation current, and provides and be the blow-off line 218 of saturation water recirculation flow.

For traditional packed bed saturex, force the major advantage of film saturex 204 to be:

(1) force the film saturex to have a quite low water cycle ratio and thereby lower energy consumption.

(2) force the film saturex to have simply a design and an operability of improving thus and reliable.

(3) force the investment cost of film saturex to be lower than the filling bed type saturex.

As shown in Figure 3, saturated raw material is by the pipe 222 of pipeline 220 to one fired heaters (Fired heater) 224, in fired heater, be preheated to 650 Fahrenheit degrees (340 degrees centigrade) in the temperature range of 1200 Fahrenheit degrees (650 degrees centigrade) by fuel, for example 1100 Fahrenheit degrees (595 degrees centigrade) with air combustion saturated raw material in well heater.Fuel 225 can be one or more exhaust flows that obtain from methanol device, the fusel oil stream 226 that for example from distiller, obtains, the flash vapor stream 228 that from ammonia synthesis loop, obtains, P SA gaseous purge stream 230 and light-end stream 232 from distiller, obtaining with air 227 incendiary.

Warmed-up saturated raw material is used to supply with part catalyzed oxidation (CPO) reactor 28 in the pipeline 234 from well heater 224, and here, it is with the oxygen described at this before or contain oxygen flow 236 and mix.This Oxygen Flow 236 from an air trap 238, obtain and preheating enamel 150 Fahrenheit degrees (65 degrees centigrade) to the temperature range of 1200 Fahrenheit degrees (650 degrees centigrade), for example 300 °F, mixed with Sweet natural gas and the steam feed that leads to the part catalyst for catalytic oxidation then.High pressure steam is used at a heat exchanger preheat oxygen.The main reaction that occurs in the part catalyst oxidation reactor 28 is a partial oxidation reaction:

And water gas shift reaction:

Fig. 6 represents that the consumption of the oxygen of aforesaid method is the function of the mol ratio of steam and carbon in the gas material, its temperature of reaction is 1600 Fahrenheit degree (870 degrees centigrade), the working pressure of 1750 Fahrenheit degrees (950 degrees centigrade) and 1900 Fahrenheit degrees (1040 degrees centigrade) and 400 pounds/square inch (gauge pressure) (2760 kPas).Can find out the consumption of oxygen from graphic representation, be expressed as the mol ratio of oxygen and carbon, for now industrial partial oxidation process, respective value of the present invention is lower, the dotted line 25 of Fig. 6 is represented minimum temperature and steam condition, that is, minimum temperature and steam carbon ratio are linear functional relation.It has been found to the sedimental generation that stops carbon in catalyzer.Usually, the reaction under the low temperature is better, for example is being about under 415 pounds/square inch (gauge pressures) (2860 kPas) pressure, and the temperature in exit is 1700 Fahrenheit degrees (925 degrees centigrade).Simply, saturex 204 provides reaching the steam of all required quantity of steam-carbon mol ratio of approximate 1.3 to 1.0, and finishes the part catalytic oxidation according to the present invention under desired temperatures and do not need other additional steam.

Fig. 7 represents that hydrogen is (with H in the product ₂Form) with the mol ratio of carbon monoxide be 1600 Fahrenheit degrees (870 degrees centigrade) in temperature of reaction, the ratio of the steam-carbon under 1750 Fahrenheit degrees (950 degrees centigrade) and 1900 Fahrenheit degrees (1040 degrees centigrade) has functional relation.

Fig. 8 and Fig. 9 are illustrated respectively in the volumn concentration of methane and carbonic acid gas in the product and are 1600 Fahrenheit degrees (870 degrees centigrade) in temperature of reaction, have functional relation between the steam to carbon ratio rate under 1750 Fahrenheit degrees (950 degrees centigrade) and 1900 Fahrenheit degrees (1040 degrees centigrade).

Figure 10 has represented the effective hydrogen (H in this method ₂) generation, be expressed as H in the product ₂With the total mole number of carbon monoxide divided by H in hydrogen and the raw material ₂With the merchant and the temperature of reaction of the total mole number of carbon be 1600 Fahrenheit degrees (870 degrees centigrade), the funtcional relationship between the steam to carbon ratio rate under 1750 Fahrenheit degrees (950 degrees centigrade) and 1900 Fahrenheit degrees (1040 degrees centigrade) condition.

Reactor effluent 244 is at first cooled off by produce steam in a boiler 246, and this boiler receives water and steam is got back in the drum from high pressure steam drum (pot) 248.This drum 248 is at a high pressure, for example about 1550Psig(10700 kPa) operation down.Supply with the water supply 250 of dry drum and at first in the coil pipe 252 of well heater 224, heat, supply with this drum by pipeline 254 then.Further heating is generating superheated vapour 260 coil pipe 258 from the steam 256 of drum 248 output, and it can be as driving steam turbine or providing heat for processing step.Pipeline 262 leads to a blow tank (not shown) to realize the blowdown of bucket 248.

Reactor effluent passes to distillation tower reboiler 266 by pipeline 264, pass to distillation tower reboiler 270 by pipeline 268, pass to softening water well heater 274 by pipeline 272, and pass to syngas cooler 278, to reclaim and the heat of utilization in synthetic gas by pipeline 276.With further cooling, for example, be cooled to 100 Fahrenheit degrees (38 degrees centigrade).Water in the process flow is condensed and this process flow passes to splitter cylinder 280, separates from synthetic gas at there water 281, and the recovery method of other cooling and heating also is operable.

After the dehydration, the hydrogen that the synthesis gas in pipeline 282 obtains from PSA unit 286 in Figure 14 is mixed in, and flows to additional compressed element 288, and there, synthetic gas is compressed into methanol loop pressure, for example, and to 1220psig(8410 kPa).Additional compressor unit among Figure 13 comprises compressor 290, and heat exchanger 292 separates splitter cylinder 294 and compressor 296, and generating supplemental air flow 298, it is sent in the methanol synthesis loop among Figure 14. Compressor 290 and 296 can be easily and the methyl alcohol circuit cycle device 302 shared in common steam turbines 300 of Figure 14.

The additional synthesis gas that obtains from compressed element 288 is in the outlet 304 and the mixed gases that circulates in the methanol synthesis loop of circulator 302.Circulation 306 is flowing to preheating in circulation heat exchanger 308 before the tubulose cooling methanol converter 312 by pipeline 310.It is when starting methanol converter that startup well heater 314 is arranged on purpose, the reaction stream of input can be heated to temperature of reaction, heated the input air-flow up to the heat that produces owing to reaction and made methanol converter enough hot, the operation that starts well heater 314 is like this ended.

Tubular cooling convertor as described in Figure 12 is a prominent feature of this method in detail, and it comprises a gas-gaseous heat exchanger that does not simply have the head pressure tube sheet.The shell 314 of container is used for keeping reaction pressure.Inlet 316 links to each other with intermediary lateral 320 by splitter 318, and next lateral 320 links to each other with many conduits 324 that extend through catalyst bed 326 vertically upward by splitter 322.Catalyst bed is bearing on the Ceramic Balls bed 328, Ceramic Balls 328 separates by pottery plate 322 and outlet 330, reactant flow is by 316 bottoms that are sent to convertor that enter the mouth, there by splitter 318, medial fascicle pipeline 320 with lead to splitter 322 shuntings of vertical tube 324.When air-flow is upwards flowed through pipeline and diverter walls by heat exchanger heats.From the outlet 334 at the conduit 324 of container top, reaction gas flow flows downward and passes catalyzer, and this catalyzer is filled in the space between the pipeline 324.The air-flow of pipeline 324 of flowing through is opposite with the air flow line of the catalyst bed of flowing through.It is quasi isothermal concentrating relative temperature range with methyl alcohol, and is very suitable with regard to speed of reaction and conversion.

The principal character of tubular cooling convertor is the simple structure of (1) this design, and there is not high pressure difference in the tubing both sides and does not have the tube plate structure problem.(2) catalyzer is filled simple.(3) only need to make a reactor and just can produce a large amount of methyl alcohol that surpasses 200 tons (1815000 kilograms) every day.(4) compare with the reactor of common guench type, the synthetic ring of methyl alcohol recycle gas flow rate has reduced.(5) heat recuperation is simplified; Can also adopt oiler feed preheating, steam rising (raising) or raw material saturated.(6) control is simplified.(7) amount of catalyzer has reduced.

With tubular type cooling convertor 322, effluent stream 330 is sent to the shell-side of forcing film saturex 204, there, comes cooling gas by heat being passed to recirculated water with pipeline 210 input gas streams of flowing through, and for example is chilled to about 340 Fahrenheit degrees (170 degrees centigrade).The convertor effluent stream is discharged inflow heat exchanger 308 from saturex by pipeline 336, discharge there air-flow with and the loop feed gas of supplying with convertor carry out heat exchange and further cooled off.Then, send into loop condenser 340 from the gas of convertor by pipeline 338, this condenser comes methyl alcohol in the steam of condensation methyl alcohol loop by water.The methyl alcohol of condensation is in separator 342 and methyl alcohol loop water sepn, and it entered pressure downwards and unload and put container 346 thick methanol steam 348 being delivered to before the distillation fraction shown in Figure 15 350 by pipeline 344.

Steam flow 354 from separator is divided into two strands, and one circulation steam flow 356 leads to the suction port of hydrokineter 302, and another burst purge stream 358 is by valve 360, and the concentration that maintains the inert material in the methyl alcohol loop is on an acceptable level.The hydrogen that reclaims from gaseous purge stream by pressure alternation absorbing unit 286 is used to produce a hydrogen recirculated air 284, and this air-flow is used for improving the stoichiometry of methyl alcohol loop steam.Flashed vapour 228 is by net 262, and gaseous purge stream 230 is taken from pressure alternation absorbing unit 286 to form a part of fuel of well heater 224.

At the distillation fraction 350 of Figure 15, thick methyl alcohol 348 is admitted to distillation tower 364, and there, the lighting end material is removed such as being absorbed gas.The overhead product 366 of tower 364 is admitted to water condenser 368 and 370, and condensation product is sent to bucket 372, and it is siphoned away by pump 374 therefrom, thereby forms the backflow to tower.The uncooled thing 232 that gently heats up in a steamer is used as fuel and is sent to fired heater.The bottom air communication of tower 364 is crossed respectively and is carried out recirculation by synthetic air and vapor heated reboiler 266 and 374, methyl alcohol stream 378 is sent to distillation tower 382 by pump 380, there, air-flow is separated into fusel oil stream 386, current 384 and finished product methyl alcohol stream 386.Distillation tower has the reboiler 270 and 388 of each free synthetic air and air-flow heating.Overhead product 389 is extracted out under vacuum by vacuum pump system 390.The steam of overhead product is by water condenser 392 condensations and sent back to separation in the bucket 394 that refluxing between the distillation tower as backflow by pump 396.Vacuum pump system 390 comprises makes water carry out round-robin pump 398 from collector 400 by water cooling heat exchanger 402.Excessive water is sent back to the bottom of distillation tower 382 from collector 400 by pipeline 404.Current 384 are extracted out from the bottom of tower 382 by pump 406, are further cooled off by heat exchanger, send into pipeline 410 then.

A process flow sheet such as a Figure 16 and shown in Figure 17 for the methanol device of low investment cost design.Hydrocarbon raw material such as Figure 17 gas flow 420, is sent to the full device 422 of raw material, and this saturex is similar to the saturex 204 among the embodiment shown in Figure 14.Water is circulated again into the top of forcing the film saturex by pump 424, and water is with the feedstream saturex pipeline of flowing through there.Saturated raw material forms saturated feedstream 425 and water, cycling stream in the bottom and the water sepn of saturex.The make up water of recirculation current is from synthesis gas condensing tower 426 and distillation residue 428.The methanol converter discharging current is sent to the shell-side of saturex to add hot water and feedstream.Pipeline 430 provides leakage path for saturex water.

As shown in figure 16, saturated raw material 425 is sent to the coil pipe 434 of fired heater 436, and full there raw material comes preheating by the burning of waste fuel 438 usefulness air 439.Be sent to catalyzing part oxidation (CPO) reactor 28 from the warmed-up saturated raw material in the pipeline 440 of well heater 436, mix with oxygen and oxygen flow 442 there and produced aforesaid synthetic gas by catalyzing part oxidation.

Reactor effluent 444 at first cools off by produce steam in boiler 446, and boiler 446 is accepted water and then steam is sent back in the drum from dry drum 448.Current in second steam drum 450 seethe with excitement in the spiral tube 452 of fired heater 436. Dry drum 448 and 450 steam output, the 454 and 456 common steam 458 that produce are used for technological process.Pipeline 460 and 462 provides passage for the boiler waste material of releasing from drum 448 and 450.Oiler feed 464 is divided into tributary 466 and 468, is sent to drum 448 and 450 separately.Tributary 466, the reactor effluent that is not sent to drum 448 as yet by pipeline 470 from boiler 446 by in pipeline 470 is heated in heat exchanger.Come the synthesis gas in pipeline 476 of automatic heat-exchanger 472 further to be cooled off by water in condenser 478, be sent to synthesis gas separator 482 by conduit 480 then, there, water of condensation 484 is extracted out by pump 486, and condensate flow 426 is provided.

After water was got rid of, the synthesis gas in pipeline 490 was compressed to the pressure in methyl alcohol loop by compressor 492, and formed a feed stream 494 of leading to desulfurization container 202.Output 496 in the desulfurization container 202 is formed for the supply gas in the methyl alcohol loop among Figure 17.

Supply synthetic gas 496 among Figure 17 adds at outlet 498 places of methyl alcohol circuit cycle device 500 in the methanol synthesis loop in the round-robin gas.Circulation 502 is before being sent to tubular type cooling methanol converter 508 by pipeline 506, by steam preheating, described methanol converter is similar to the tubular type cooling methanol converter 312 among Figure 14 basically in heat exchanger 504.When the initial start methanol converter, the pipeline 510 of drawing from loop well heater 504 is sent to warmed-up loop gas at the top of convertor 508.

The air-flow 512 of deriving from tubular type cooling convertor 508 is sent to the shell-side of forcing film saturex 422, and there, the heat of gas is passed to the recirculated water neutralized stream in the natural airflow of the input of saturex and cooled off.The discharge gas of convertor leaves in the saturex by pipeline 514, delivers to water condenser 516 then and sentences methyl alcohol in the condensation methyl alcohol loop stream passage 518.Condensed methyl alcohol is separated from the methyl alcohol loop in separator 520, is sent in the pressure release container 526 by pipeline 522 and valve 524 then.

The air-flow 528 of output is divided into two strands from separator 520, and one is the recirculated air 530 that is sent to the suction side of hydrokineter 500, and another strand is by valve 534, keeps the gaseous purge stream 532 of the concentration of the inert material in the methyl alcohol loop in an acceptable level.Merge the waste fuel stream 488 that is formed for fired heater 436 from the flash gas 536 of the container 526 of releasing with gaseous purge stream 532 by valve 538.

Be sent to distillation tower 542 from the thick methyl alcohol 540 of container 526 outputs of releasing, there, air-flow is separated into light ends stream 544, one current 546 and finished product methyl alcohol stream 548.Distillation tower has one by steam-heated reboiler 550.Overhead product 552 is cooled off by water condenser 554, produces the methyl alcohol stream 556 of a condensation, and wherein a part is used for refluxing by pump 558.The rest part of condensation methyl alcohol stream 556 mixes formation product flow 548 with potato spirit part 560.Current 546 from 542 ends of tower cool off in water cooler 562, and are sent to the air-flow 428 that leads to saturex 422 by pump 564.

Following examples will further be explained the present invention described herein, but be construed as limiting the invention never in any form.

Just like the methanol device day shown in Figure 13,14 and 15 handling 2000 tons of (1,800,000 kilogram) methyl alcohol.Under tabulate I, II and III listed be used for the device mole/hour, molar content and pressure parameter, temperature, water/steam and heat passage.Mole/hour be pound-mol/hour (0.4536 kilogram mole/hour).

Table I (continuing)

Mole number/hour

CH is described ₃OH C ₄H ₉OH CH ₃OCH ₃Summation

Natural (coal) gas 6255.4

(circuit 200)

Saturated natural (coal) gas 14559.1

(circuit 220)

Oxygen 3202.1

(circuit 236)

Catalytic partial oxidation reactor outlet 25908.3

(circuit 244)

The loop replenishes 19186.7

(circuit 298)

Converter import 492.2 1.0 30.7 120836.8

(circuit 310)

Converter exports 5787.0 8.1 37.8 110162.0

(circuit 330)

Isolating liquid 5287.3 7.1 6.6 6977.8

(circuit 344)

Gas separated exports 499.7 1.0 31.2 103184.2

(circuit 354)

Loop recirculation 492.2 1.0 30.7 101650.1

(circuit 356)

Discharge gas 7.5 0.5 1534.1

(circuit 358)

The hydrogen 607.8 of pressure alternation adsorber

(circuit 284)

The discharge 7.5 0.5 926.3 of pressure alternation adsorber

(circuit 230)

Flash gas 6.5 0.4 167.3

(circuit 228)

Thick methyl alcohol 5280.8 7.1 6.2 6810.5

(circuit 348) (NO)

Table II (continuing)

Molecular fraction

H is described ₂O CH ₃OH C ₄H ₉OH CH ₃OCH ₃

Natural (coal) gas

(circuit 200)

Saturated natural (coal) gas 57.04

(circuit 220)

Oxygen

(circuit 236)

Catalytic partial oxidation reactor outlet 28.41

Circuit 244)

The loop replenishes 0.16

(circuit 298)

Converter import 0.05 0.41 0.03

(circuit 310)

Converter exports 1.36 5.25 0.01 0.03

(circuit 330)

Isolating liquid 21.05 75.78 0.10 0.09

(circuit 344)

Gas separated exports 0.02 0.48 0.03

(circuit 354)

Loop recirculation 0.02 0.48 0.03

(circuit 356)

Discharge gas 0.02 0.48 0.03

(circuit 358)

The hydrogen of pressure alternation adsorber

(circuit 284)

The discharge 0.04 0.81 0.05 of pressure alternation adsorber

(circuit 230)

Flash gas 0.18 3.89 0.24

(circuit 228)

Thick methyl alcohol 21.56 77.54 0.10 0.09

(circuit 348)

Because to the embodiment of above statement, can make many detailed improvement, conversion and change do not depart from scope and spirit essence of the present invention, so the accompanying drawing and the note that show are to further specify of the present invention, rather than place restrictions on its connotation.

Claims (22)

1, a kind of method for preparing methyl alcohol, it is characterized in that this method comprises: the hydro carbons raw material of (or claiming hydrocarbon polymer), oxygenant and optional steam form a kind of uniform gaseous mixture, wherein oxygen is in 0.4: 1 to 0.8: 1 scope to the mol ratio of carbon, and steam is in 0: 1 to 3.0: 1 scope to the carbon mol ratio, part catalyzed oxidation said mixture, this part catalyzed oxidation is to be equal to or greater than under the minimum temperature of selecting in temperature to carry out, this selected temperature is selected according to a kind of linear functional relation, corresponding to steam to the carbon mol ratio from 0.4: 1 to 0: 1, and the temperature range that above-mentioned funtcional relationship relates to is from 870 ℃ to 1040 ℃, thereby generation hydrogen, a kind of synthetic gas of carbon monoxide and carbonic acid gas, under preparation methyl alcohol condition, make hydrogen, carbon monoxide and carbonic acid gas react, and isolate (or claiming to reclaim) methyl alcohol then.

2, according to a kind of preparation method of claim 1 defined, it is characterized in that described reaction gas mixtures by making the cumulative volume that synthesis gas uses catalyzer by hydrocarbon raw material, its space velocity is from 20,000 hours ^-1By 500,000 hours ^-1In the scope.

3, according to a kind of preparation method of claim 1 defined, it is characterized in that described part catalyzed oxidation be steam to the carbon molecular ratio from 0.8: 1 to 2.0: 1 and oxygen the molecular ratio of carbon is carried out in 0.45: 1 to 0.65: 1 scope.

4, according to a kind of preparation method of claim 1 defined, the oxygenant that it is characterized in that part catalyzed oxidation step is the oxygen rich gas that contains at least 70 moles of % oxygen.

5, according to a kind of preparation method of claim 1 defined, the oxygenant that it is characterized in that part catalyzed oxidation step is the oxygen rich gas that contains at least 90 moles of % oxygen.

6,, it is characterized in that the oxygenant of part catalyzed oxidation step is an air according to a kind of preparation method of claim 1 defined.

7,, it is characterized in that the part catalysed oxidn occurs between 760 ℃ to 1260 ℃ of the temperature according to a kind of preparation method of claim 1 defined.

8,, it is characterized in that the part catalysed oxidn occurs between 870 ℃ to 1090 ℃ of the temperature according to a kind of preparation method of claim 7 defined.

9, according to a kind of preparation method of claim 1 defined, it is characterized in that carrying out methyl alcohol synthetic gas and will handle and regulate the mol ratio of hydrogen, make this mol ratio (H2)/(2CO+3CO2) have value to be at least 0.8 carbon monoxide and carbonic acid gas summation.

10,, it is characterized in that described mol ratio (H according to a kind of preparation method of claim 9 defined ₂)/(2CO+3CO ₂) have value and be at least between 0.90 and 1.1.

11,, it is characterized in that described mol ratio (H according to a kind of preparation method of claim 9 defined ₂)/(2CO+3CO ₂) be to regulate by adding the hydrogen that reclaims in the sweeping gas by the methyl alcohol loop.

12,, it is characterized in that described mol ratio (H according to a kind of preparation method of claim 9 defined ₂)/(2CO+3CO ₂) be by adding methyl alcohol, the hydrogen that reclaims in the combination of sweep gas and the synthetic gas that produced by the part catalyzed oxidation is regulated.

13,, it is characterized in that present method is to use pressure film saturex to reclaim by the synthetic reaction heat that produces of methyl alcohol according to a kind of preparation method of claim 1 defined.

14,, it is characterized in that present method is to use tubular type refrigerative converter to be prepared the reaction of methyl alcohol according to a kind of preparation method of claim 1 defined.

15,, it is characterized in that present method is to use single packed column to prepare purified methyl alcohol in order to distill thick methyl alcohol according to a kind of preparation method of claim 1 defined.

16, a kind ofly prepare the method for methyl alcohol by hydrocarbon raw material, this method comprises:

(a) mixed gas of basic blended hydrocarbon raw material, oxygen or oxygen-containing gas fully and optional steam is added the zone of part catalysed oxidn, wherein steam is 0: 1 to 3.0: 1 to the carbon molar ratio range, and oxygen is 0.4: 1 to 0.8: 1 to the carbon molar ratio range, this mixed gas is to be not less than 93 ℃ in temperature, but be lower than and add under the spontaneous ignition temperature of catalyzer

(b) in part catalyzed oxidation zone hydrocarbon raw material being carried out partial oxidation by the catalyzer that makes hydrocarbons can carry out partial oxidation with mixed gas generates mainly by methane, carbon oxides, a kind of gas of hydrogen and vapor composition, the geometrical surface that above-mentioned catalyzer has is 5cm at least to volume ratio ²/ cm ³And have corresponding to space velocity 20,000 hours ^-1Thereby cumulative volume produces hydrogen, a kind of synthesis gas of carbon monoxide and carbonic acid gas,

(c) under preparation methyl alcohol condition, make hydrogen, carbon monoxide and carbonic acid gas react and

(d) reclaim methyl alcohol.

17,, it is characterized in that steam is to the mol ratio of carbon in 0.8: 1 to 2.0: 1 and oxygen are scope at 0.45: 1 to 0.65: 1 to the mol ratio of carbon according to a kind of preparation method of claim 16 defined.

18, according to a kind of preparation method of claim 16 defined, the reaction that it is characterized in that preparing methyl alcohol be temperature from 210 ℃ to 302 ℃ scope, reactant with contain zinc oxide and contact down with copper oxide catalyst and carry out.

19, according to a kind of preparation method of claim 16 defined, it is characterized in that carrying out methyl alcohol synthetic gas and will handle and adjust the mol ratio of hydrogen carbon monoxide and carbonic acid gas summation, make this mol ratio (H ₂)/(2CO+3CO ₂) have value and be at least 0.8.

20,, it is characterized in that described mol ratio (H according to a kind of preparation method of claim 19 defined ₂)/(2CO+3CO ₂) have value between about 0.95 and 1.1.

21, a kind ofly prepare the method for methyl alcohol by the hydrocarbons gas that mainly contains methane, this method comprises:

(a) be scope with steam from 0: 1 to 3.0: 1 to the carbon mol ratio, oxygen does not have the following hydrocarbon gas of incendiary condition and mixes with steam and oxygen containing gas in that mixing only is provided 0.4: 1 to 0.8: 1 scope of carbon mol ratio,

(b) the part catalysed oxidn with the catalyzer that can make methane part catalyzed oxidation the zone in the gas of hydrocarbon polymer, the gaseous mixture of steam and oxygen carries out partial oxidation, and above-mentioned catalyzer has the geometric area zone ratio of volume is at least 5cm ²/ cm ³With one corresponding to space velocity 20,000 to 500,000 hours ^-1Cumulative volume, thereby make a kind of hydrogen, the synthesis gas of carbon monoxide and carbonic acid gas,

(c) the preparation methyl alcohol condition under hydrogen, carbon monoxide and carbonic acid gas are reacted and

(d) reclaim methyl alcohol.

22, according to a kind of preparation method of claim 21 defined, it is characterized in that the part catalysed oxidn be steam to the molecular ratio of carbon from 0.8: 1 to 2.0: 1 and oxygen the molecular ratio of carbon was carried out in the scope from 0.45: 1 to 0.65: 1, the oxygenant of part catalyzed oxidation step is the oxygen rich gas that contains at least 70 moles of % oxygen, and the part catalysed oxidn is that 870 ℃ to 1090 ℃ scopes take place in temperature.

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