CN1607977A

CN1607977A - An optimized gas solid phase catalytic reaction method and apparatus

Info

Publication number: CN1607977A
Application number: CN02826254.9A
Authority: CN
Inventors: 楼韧; 楼寿林
Original assignee: Individual
Current assignee: Hangzhou Linda Chemical Technology Engineering Co ltd
Priority date: 2001-12-28
Filing date: 2002-12-30
Publication date: 2005-04-20
Anticipated expiration: 2022-12-30
Also published as: AU2002357566A1; CN100486685C; WO2003055586A1

Abstract

A method and apparatus for optimizing the gas solid-phase catalytic reaction under pressure, wherein a reactor is composed of a self heating reactor and a separately cooling reactor. Such two kinds of reactors are continuous heat exchange reactors, and are associated with each other in succession. Firstly, gases react in the self heating cold pipe reactor at balanced temperature, and catalyst layer is cooled with synthetic gas to transfer heat. Then, in the separately cooling reactor, the catalyst layer is cooled with water to reover heat of the reaction, and to make the temperature of the latter reactor lower than the front reactor. Increased reaction conversion rate, reactant concentration, and productivity are achieved. The present invention has the advantages of optimized reaction temperature, simple structure, good operating performance and reduced investment.

Description

An optimized gas solid phase catalytic reaction method and apparatus

A kind of field for optimizing the invention of gas-solid catalysis method and apparatus

The present invention is a kind of gas-solid catalysis method and apparatus, for fluid catalyst reaction and diabatic process, belong to field of chemical engineering, be particularly suitable for methanol synthesis reaction process, it can also be used to the chemical process such as methyl ether, methylamine, ammonia, methane, carbon monodixe conversion.The background of invention

For converting this kind of gas-solid phase exothermic catalytic reaction by pressurization lower methanol-fueled CLC, methylamine, methyl ether, ammonia synthesis and CO, with the progress of course of reaction, the reaction heat constantly released improves catalyst layer temperature.In order to improve the efficiency of reactor, it is necessary to reaction heat be removed to reduce reaction gas temperature.Once widely used one kind is multistage insulation reaction in industrial reactor, reaction gas temperature is reduced between two sections with unstripped gas cold shock, reactant concentration is also reduced while reaction gas temperature is lowered when this reactor is because of unstripped gas cold shock, synthetic ratio is have impact on.Another shell and tube reactor of German Lurgi companies for methanol-fueled CLC, catalyst is housed, unstripped gas is from upper inlet port into being distributed to each pipe in many pipes on having in pressure shell between lower perforated plate, pipe, lateral inflow between the synthesizing methanol in the built-in catalyst layer of pipe, pipe.Reaction tube continuously moves heat by boiled water outside pipe, produces steam and is gone out by lateral tube, reaction gas goes out tower by bottom escape pipe, and the tower temperature difference is small, but catalyst filling coefficient is small, investment is big.SPC structure of reactor disclosed in USP4767791 of Japanese Mitsubishi companies etc. is that the pipe in above-mentioned shell-and-tube reactor is changed into concentric tubes, catalyst is mounted between inner and outer pipes, inner tube is used as catalyst layer reaction gas countercurrent flow outside cold air path and inner tube, to reduce the reaction temperature of catalyst layer latter end, synthetic ratio is improved, but this spline structure is more complicated.

The characteristics of task of the present invention is according to Gas-solid phase catalytic exothermic reversible reaction, the characteristics of overcoming prior art provides that a kind of catalyst layer Temperature Distribution is reasonable, catalyst activity is high, simple and reliable for structure, good operation performance reactor and a kind of method for meeting optimum response.The general introduction of invention

The present invention mainly realizes purpose by following improved method, i.e. by gas-solid phase exothermic catalytic reaction first with self-heating reaction i.e. with entering tower unstripped gas reaction heat in catalyst layer outside absorption tube in cold pipe, make to reach reaction temperature into tower gas simultaneously, then enter catalyst layer reaction.Then enter external-cooling type reactor again, use cooling agent（Such as water）Indirect heat exchange absorbing reaction heat simultaneously produces steam.This kind of self-heating and outer cold heat exchange reaction bonded, can make rear portion reaction keep the temperature more relatively low than above, this can improve synthesising reacting speed to this kind of heat release reversible reaction of such as methanol-fueled CLC, improve methanol-fueled CLC rate.The gas-solid catalysis method and apparatus of the present invention mainly has gas-solid mutually to confirm this Exothermic catalytic reaction device 1, by self-heating 1A and bis- kinds of Continuous Heat Transfer reactors of external-cooling type 1B are front and rear combined constitutes, self-heating reactor 1A is by bearing shell P, by gas in pipe can on, the set of heat exchange tubes of lower flowing into cold tube bag Cb and catalyst K constitute, heat exchanger tube has port, pipe is inside and outside to be connected, external-cooling type reactor 1B is by bearing shell P, set of heat exchange tubes Cd and catalyst K is constituted, do not connected inside and outside heat exchanger tube, reactor 1, heat recoverer 2, the gas heat exchanger 3 of gas one, reaction product cools down condenser 4, separator 5, link composition serialization industrial installation with pipeline before and after the grade of gas compression cycle machine 6, first absorbing reaction is hot in reactor 1A autothermic reactor cold tube bags Cb for gas, reaction temperature is heated to react into catalyst layer outside pipe again, external-cooling type reactor 1B is arrived again passes through set of heat exchange tubes Cd cooling medium continuous absorption reaction heat, go out reactor hot gas and reclaim heat through heat recoverer 2, exchanged heat through the gas heat exchanger 3 of gas one with entering cold air before reactor, cool down the cooling reaction gas condensation reaction product of condenser 4, the separation product of separator 5, gas after separation product is in addition to a part is discharged, major part is mixed after removing the pressure-raising of circulator 6 with unstripped gas, heated in the gas heat exchanger 3 of gas one into reactor reaction, external-cooling type reactor 1B set of heat exchange tubes Cd is by one or more groups of cold tube bag Cd Cd₂... coaxial package is constituted, and every group of cold tube bag is by coolant inlet pipe_ai, lower endless tube be isocon and cold pipe b, upper endless tube i.e. header, outlet composition, inlet tube and the dizzy i.e. isocon d of lower ring, outlet and upper endless tube are header connection, cold pipe b and up and down endless tube connection, and cooling medium is by inlet tube_ai、 a₂Enter, then by isocon d, C₂It is diverted in each cold pipe b, flows to header, d₂Concentrate, by outlet E₂Outflow, gas is entered by housing P upper ports, is reacted through catalyst layer outside cold pipe group, reaction heat is absorbed by cooling medium in cold pipe b, gas to bottom gas outlet G₂Dress catalyst P h are arranged at outlet, reactor top, and the porous support grid of catalyst is arranged at bottom（R) .The 0. 5 0. 8 of the catalyst total amount that the catalytic amount filled in self-heating inner-cooled reactor is filled by total reactor.

Reactor 1B can be cooling agent in pipe, the cold pipe of cold pipe group, can be circular straighttube, flat tube, can also be snakelike pipe, spiral shape pipe, many elbow U-tubes, can also cooling agent between shell, built-in catalyst is managed, this transformation to existing apparatus can utilize original shell-and-tube reactor.Brief description

It is further described below in conjunction with the accompanying drawings.

Fig. 1 is the general flow chart of the present invention.

Fig. 2 is another stream standing grain of the present invention in figure.

Fig. 3 is the external-cooling type byproduct steam reactor sketch of the present invention.

Fig. 4 is the external-cooling type byproduct steam radial reactor sketch of the present invention. '

Fig. 5 is axial flow reactor sketch of the self-heating with outer cold combination of the present invention.

Fig. 6 is Radial Flow reactor sketch of the self-heating with outer cold combination of the present invention. The detailed description of invention

The present invention is described in detail by taking methanol-fueled CLC as an example below, the recovery of wherein reaction heat is passed through cooling agent and produces steam and realize.In the following example using water as the example of cooling agent, but this example is non-limiting, it will be understood by those skilled in the art that in addition to water can also be using various known cooling agents.

In Fig. 1, there are inner-cooled reactor 1A and external-cooling type reactor 1B tandems, there is waste heat boiler 2, the gas heat exchanger 3 of gas one, water cooler 4, methanol separator 5 and recycle compressor 6, front and rear pipeline links composition methyl alcohol product installation.Converging containing hydrogen and raw material of carbon oxide gas 7 into methanol synthesizer and the circulating air 12 from circulator 6 for gaseous mixture 8 for 3 ~ 32MPa is compressed to through compressor, enter reactor 1A to 100 °C or so with reaction gas heat exchange through the gas heat exchanger 3 of gas one, reactor 1A can use the published patent of such as inventor " W00191894 ", can also use other self-heating cold-tube type structures.Enter reaction heat of the synthetic tower gas in cold pipe outside absorption tube in catalyst layer, temperature is increased to 200 °C or so and goes out cold pipe, into pipe outside react in catalyst layer.Due to continuously moving heat by gas in cold pipe, therefore the relatively low temperature difference of catalyst layer is kept, go out C 0H in reactor 1A reaction gas and reach 6% or so, temperature 25.CTC or so, enter back into reactor 1B external-cooling types reactor and further carry out methanol synthesis reaction.Reaction heat is by cooling agent（Such as water）Continuously removed by tube wall, reaction heat can be used for the middle pressure steam for producing pressure 4MPa or so, reaction temperature can conveniently be adjusted by the pressure of reactor byproduct steam, therefore reactor 1B reaction temperature can be made to be less than anterior reactor 1A, such as 210 °C or so, to optimize reaction temperature process conditions, synthetic ratio is improved, reactor methanol concentration is used and brings up to 10% or so.Go out reactor 1B reaction gases 9 and reclaim reaction heat through heat regenerator outside tower 2, by-product low-pressure steam, heated again in the gas heat exchanger 3 of gas one into gas reactor 8, then reaction gas, which is entered back into, is further cooled to 30 °C or so in water cooler 4, the methanol overwhelming majority in reaction gas is condensed.Cold reaction gas, which enters in methanol separator 5, carries out gas-liquid separation, product methanol is sent out by bottom through pipe 13, unreacting gas 10 are by upper outlet, wherein sub-fraction is made off-gas and discharged by pipe 11', to maintain inertia Gas content in synthesis system will not be too high, most of gas 12 converges for gas 8 after being boosted through circulator 6 with unstripped gas 7, and dereaction device starts to circulate again again.In Fig. 1, boiler water is entered by lower tube 14 in reactor 1B, and the middle pressure steam of generation is drawn by upper tube 15.Pipe 15 connects drum.Boiler water is sent into by pipe 16 in heat regenerator 2, and the low-pressure steam of generation is drawn by 17, and cold water is introduced by pipe 18 in water cooler, by 19 discharges.

Fig. 2 is another flow chart.Removed in figure and reactor 1A and 1B in Fig. 1 are merged into one, reactor

1 is made up of top self-heating and bottom external-cooling type reactor, and bottom external-cooling type reactor is the hot heat exchanger tube for having multiple u-shaped elbows, and other are same as in figure 1.

Fig. 3 is external-cooling type reactor sketch.Set of heat exchange tubes Cd is housed in pressure shell P, catalyst K is housed, set of heat exchange tubes Cd is by two groups of cold tube bag Cd Cd between shell P and set of heat exchange tubes Cd₂Composition, every group of cold tube bag.^ is by isocon（Lower endless tube）C, multiple rows of cold pipe header（Upper endless tube）Connect and compose.Cold pipe B connection isocons and header, isocon connection inlet tube_ai, header connection outlet pipe 5₁Link through housing and external pipe.Outlet can use elastic hose or ripple Pattern pipes etc., cold tube bag Cd₂Also such as dl, outlet E_t、 E₂Individually can draw outside reactor enclosure, also can as converging in figure in reactor after by export f go out.F position can as in figure side, can also in upper cover crown center, and by air inlet ^ be arranged on side.Reactor head has air inlet G_{1 5}Gas outlet G is arranged at bottom₂.Gas outlet G₂Manhole h is additionally provided with to support the catalyst K in reactor, top provided with porous cone-shaped hood ^, for filling catalyst and making access hole.When with this reactor be used as methanol-fueled CLC byproduct steam when, it is preheated to 200 or so boiler water by inlet tube a_t, introduce bottom isocon d, C₂, then uniform divided flows are into each cold pipe b.Water in cold pipe while to outside upper one side absorption tube reaction heat, vaporization of being heated produces steam, then by top header, d₂Converge, ' by outlet Ei, E₂Draw, temperature enters tower gas by air inlet G air inlets for more than 200 °C, reacts into methanol catalyst layer K.Reaction heat is absorbed by water in pipe, therefore the catalyst layer temperature difference is small.

Fig. 4 is external-cooling type radial reactor sketch.Set of heat exchange tubes is similar with multigroup set of heat exchange tubes in Fig. 3 in Fig. 4.From unlike Fig. 3, columnar porous dividing walls L is provided with shell P inner side, annular inlet channel is formed between dividing walls L tops and shell P, porous discharge m is provided with center.Gas enters after reactor and to enter catalyst layer K in dividing walls L, radially flowing reactive, and gas enters after discharge by outlet G to discharge m stomatas after reaction₂Go out tower, Fig. 4 bottoms also have catalyst to unload outlet n, other marks and Fig. 3-sample.

External-cooling type reactor in Fig. 3, Fig. 4 can be used for the endothermic reaction, such as methane conversion, the hydrocarbon pyrolysis.At this moment through inlet tube_aiWhat it is into set of heat exchange tubes Cd is heating agent, and the heat that the endothermic reaction is carried out in reactor 1B is supplied by the heating agent in set of heat exchange tubes Cd.

Fig. 5 is by the reactor sketch of a kind of interior cold and outer cold combination.Top is self-heating inner-cooled reactor, and bottom is external-cooling type.There is same bearing shell P above and below reactor, there is interior cold cold tube bag Cb in the autothermic reactor housing of top, cold tube bag Cb has gas-distributing pipe 0, the multigroup cold pipe b of gas-distributing pipe Q connections, , cold pipe bi can be U-tube, another end opening of U-tube, gas-distributing pipe Q is connected with air inlet pipe S, air inlet pipe S connects sub-air chamber and lower section gas-distributing pipe Q above dividing plate through dividing plate J, also can be without dividing plate, each air inlet pipe S leads directly to shell P opening air inlets, cold tube bag can be supported on barrel P by support plate T, cold reactor has set of heat exchange tubes Cd outside bottom, set of heat exchange tubes Cd can be made up of the straight tube in such as Fig. 3, except that the header in set of heat exchange tubes Cd is connected with escape pipe E, pipe E connects outlet by upper reactor catalyst with dividing plate J.Catalyst K is being housed up and down, catalyst is supported into continuous bed with bottom porous screen R, and reactor head has air inlet G, and gas outlet G is arranged at bottom between cold tube bag Cb, set of heat exchange tubes Cd and housing P₂, synthesis gas is by top air inlet G₁Into reactor, it is evenly distributed to through air inlet pipe S through dividing plate J by top cold tube bag Cb to gas-distributing pipe Q in the cold pipe of each shape, reaction heat in the outer catalyst layer of absorption tube, it is warming up to 200 or so, cold pipe is gone out into catalyst layer by the cold pipe 1^ other ends top of U-shaped, flow downward, react while into cold pipe gas heat-transfer, until going out interior cold conversion zone Catalyst enters cold conversion zone catalyst outside bottom, continues the reaction that flows downward, and the cooling agent boiler boiling water that reaction heat is delivered in set of heat exchange tubes Cd herein produces Steam Recovery heat, and until bottom, reaction gas is through G₂Outlet.It is heated to 20CTC or so boiler feedwaters and is diverted to each cold pipe b into isocon C by inlet tube a₂In, the steam of generation is collected by discharge d to flow out through outlet E.Set of heat exchange tubes Cd group number can increase and add according to reactor diameter in above-mentioned Fig. 3 ~ Fig. 5. ·

Cold pipe is that set of heat exchange tubes can also be the pipe group of coiled pipe, spiral element and multiple return bends in straight tube is constituted outside the cold reactor with outer cold combination in addition to this bottoms of Fig. 5.When being multiple return bends, reactor 1 in the structure such as Fig. 2 of this interior cold and outer cold combined reactor, cold self-heating structure is similar to Fig. 5 in top, bottom is the U-tube group of many elbows, entered by bottom water inlet pipe 14, boiler water enters the heated boiling of the outer reaction heat of absorption tube in shape pipe, produces steam and is flowed out by side exit pipe 15.

Fig. 6 is the radial reactor by cooling type and internally cooled coaxial package, and outside portion is self-heating inner-cooled, and inside portion is external-cooling type, has porous dividing walls L close to cylinder inboard wall Ρ inwalls, there is porous discharge m at center.Reactor, which has in same bearing shell p, outside portion autothermic reactor housing, has interior cold cold tube bag Cb, cold tube bag Cb to have gas-distributing pipe, discharge Q₂, the multigroup cold cold pipes of pipe bu point descending cold pipe and the up cold pipe of gas-distributing pipe connection, descending cold pipe connection gas-distributing pipe and discharge, the up cold lower endless tube Q of pipe end connection₂, one end open.Gas-distributing pipe is connected with air inlet pipe S, and cold reactor has the header mountain in set of heat exchange tubes Cd, set of heat exchange tubes Cd to be connected with escape pipe E outside interior sorrowful portion, and isocon is connected with air inlet pipe, and multigroup cold pipe b is connected with isocon ^ and header.Catalyst K is housed between inside and outside cold tube bag Cb, the set of heat exchange tubes Cd of dividing walls L and header, reactor head has air inlet G₁₅Gas outlet G is arranged at bottom₂, reacted through interior cold and outer cold catalyst layer K by L to m Radial Flows after gas elder generation.

Using it is also possible to apply the invention to unstripped gas multistep reaction, for example use synthesis gas preparing dimethy ether, the armoring alcohol catalyst in previous autothermic reactor, synthesis gas reaction is set to generate methanol, methanol dehydration catalyst is filled in latter reactor, methanol is generated into dimethyl ether again, in another example with the indirect legal system gasoline of synthesis gas, synthesis gas reaction is generated methanol and dimethyl ether with bifunctional catalyst in previous autothermic reactor, such as zeolite catalyst methanol and dimethyl ether mixture is loaded in latter outer cold reactor and is then converted to gasoline.. .

Using the present invention, synthetic reaction gas once passes in and out reactor, device structure is simple and reliable, catalyst is outside heat exchanger tube, catalyst filling coefficient ratio Lurgi shell-and-tubes and Japan SPC are big, and it is low to enter gas reactor temperature, the gas heat exchanger area of reduction tower outer gas one, with outer cold reactor import coolant temperature flexible modulation and reaction rear part temperature is reduced, improve synthetic ratio.Embodiment

With hydrogen, carbon oxide feed gas synthesizing methanol, synthesis pressure 7MPa, using in the present invention it is cold with it is outer cold Combined reactor, with domestic NC306 copper-based methanols catalyst 20M³, wherein 12M in interior cold reactor³, 8M in outer cold reactor³, enter tower gas 982Kmol/h, enter exhaust gas composition and see the table below.

From table, sequence number 1 is shown in using composition during the present invention, goes out methanol column CH₃0H is 10. 4%, ' yield is the ton per day of ' 600, and sequence number 2 is seen using usual methanol synthetic tower result, is equally entering tower tolerance and into going out methanol column CH under divided working status₃0H is 8. 26%, ' the ton per day of methanol output 503, using output increased 19% of the present invention.

Claims

Claim

1. a kind of equipment for pressurization catalytic reaction, it includes：Reactor（1), heat exchanger（2,3,4), separator（5) with compression circulator（6) ;

The reactor（1) connected self-heating inner-cooled reactor is included（1A) with external-cooling type reactor（1B), the self-heating inner-cooled reactor（1A) by bearing shell（P) and in pipe gas can upper and lower different directions flowing the heat exchanger tube (cold tube bag that bj is constituted（Cb) constitute, cold tube bag (Cb) places catalyst outside（K), heat exchanger tube has one end open top, and pipe is inside and outside to be connected；

The external-cooling type reactor（1B) by bearing shell（) and set of heat exchange tubes P（Cd) constitute, set of heat exchange tubes (Cd) places catalyst outside（K), do not connected inside and outside heat exchanger tube； '

The reactor（1) gas outlet by pipeline successively with heat exchanger（2), ' heat exchanger（3), heat exchanger (4), separator（5) circulator, is compressed（6), heat exchanger（3), reactor（1) air inlet is connected.

2. equipment as claimed in claim 1, it is characterised in that the external-cooling type reactor（Set of heat exchange tubes 1B)（Cd it is) by one or more groups of cold tube bags（Cd Cd₂……）Coaxial package is constituted, every group of cold tube bag（Cd is isocon by coolant inlet pipe, lower endless tube（D) with cold pipe（B), upper endless tube is header（）, outlet composition, inlet tube（) and lower endless tube（D), outlet（EJ and upper endless tube（D) connect, cold pipe（B) with upper and lower endless tube（）, (d) connection.

3. equipment as claimed in claim 1 or 2, it is characterised in that the external-cooling type reactor（1B) close to cylinder inboard wall（P) there are porous dividing walls（U, L upper end and shell（P annular inlet channel is formed between), there is porous discharge at center（M), gas is in catalyst layer（K in) by（L) arrive（M) radially flowing reactive.

4. equipment as claimed in claim 1, it is characterised in that the reactor（1) top is self-heating inner-cooled reactor（1A), bottom is external-cooling type reactor（IB), there is same bearing shell above and below reactor（P) ；The top self-heating inner-cooled reactor（1A) there is interior cold cold tube bag in housing（Cb), cold tube bag（Cb) there is gas-distributing pipe（Q), gas-distributing pipe（Q multigroup cold pipe) is connected（Bj, cold pipe（B is U-tube, another end opening of U-tube, gas-distributing pipe（) and air inlet pipe Q（S) connect, air inlet pipe（S dividing plate) is passed through（J) sub-air chamber and lower section gas-distributing pipe above connection dividing plate（Q), manage（) and dividing plate S（J by stuffing-box movable sealing between), cold tube bag can be by support plate（T) it is supported on barrel（P on)；

Cold reactor outside the bottom（1B) there is set of heat exchange tubes（Cd), set of heat exchange tubes（Cd header and escape pipe in)（E) connect, isocon（C) and air inlet pipe（_ai) connection, multigroup cold pipe（And isocon b)（And header d)（Dj connections, escape pipe（E upper reactor dividing plate) is passed through（J outlet tube) is connected, in cold tube bag up and down（Cb), set of heat exchange tubes（) and housing Cd（Catalyst is housed between P)（K), From top to lower catalytic agent into continuous bed, by bottom porous screen（R) support, reactor head has air inlet（G_t), gas outlet is arranged at bottom（G₂) 。

5. equipment as claimed in claim 4, it is characterised in that the cold pipe group (Cd) of bottom external-cooling type reactor is the cold pipe group of multiple return bends.

6. equipment as claimed in claim 1, it is characterised in that the reactor（1) it is to have porous dividing walls (L) close to cylinder inboard wall (P) inwall, there is porous discharge at center（M), constitute（L) and（M) the Radial Flow reactor of cold and outer cold coaxial package between, outside portion is self-heating inner-cooled reactor（1A), inside portion is external-cooling type reactor（1B), reactor（1A) and（IB) there is same bearing shell（P ) ；

The outside portion autothermic reactor（1A) there is interior cold cold tube bag in housing（Cb), cold tube bag（Cb) there is gas-distributing pipe（QJ, discharge（Q₂), gas-distributing pipe（The multigroup cold pipe of QJ connections（Bj, cold pipe（T) descending cold pipe and up cold pipe, descending cold pipe are divided（Bj connection gas-distributing pipes（Q and discharge（Q₂), the up cold lower endless tube of pipe one end connection（Q₂), one end open, gas-distributing pipe and air inlet pipe（S) connect；

Cold reactor outside the inside portion（IB) there is set of heat exchange tubes（Cd), set of heat exchange tubes（Cd header (d.) and escape pipe in)（E) connect, isocon（And air inlet pipe d)（_ai) connection, multigroup cold pipe（And isocon b)（And header d)（Dj connections, in inside and outside cold tube bag（Cb), set of heat exchange tubes（) and housing Cd（Catalyst is housed between P)（K), reactor head has air inlet（Gas outlet is arranged at G, bottom（G₂), through interior cold and outer cold catalyst layer after gas elder generation（K) by（L) arrive（M) Radial Flow is reacted.

7. the equipment as any one of claim 1-4, it is characterised in that the catalytic amount filled in the inner-cooled reactor accounts for reactor fills catalyst total amount 0. 5 0. 8. -

8. equipment as claimed in claim 1, it is characterised in that described to be connected to from inner-cooled reactor（External-cooling type reactor after 1A)（IB) it is a kind of heat exchanger tube apparatus with catalyst inside, to remove the shell-and-tube reactor that the cooling agent of reaction heat flows between shell.

9. equipment as claimed in claim 1, it is characterised in that the self-heating inner-cooled（1A) with external-cooling type (1B) with self-heating inner-cooled reactor（1A) in preceding, external-cooling type reactor（1B) posterior mode is connected by connecting pipe, external-cooling type reactor（Reaction temperature in 1B) is than anterior self-heating reactor（70 °C of the low 10- of reaction temperature in 1A)_o

10. one kind carries out pressurization catalytic reaction side's methods using equipment as claimed in claim 1, it in turn includes the following steps：

(1) mixed material gas is made（8) in self-heating inner-cooled reactor（Enter after reaction heat in cold pipe 1A) in the outer catalyst layer of absorption tube and manage outer catalyst layer reaction, form Primary product；

(2) Primary product is made to enter external-cooling type reactor（1B) further reacted, remove reaction heat with cooling agent during the course of the reaction, adjust reaction temperature, form reactant mixture；

(3) separation product from the reactant mixture.