CN105658617A

CN105658617A - Hydrogenation of dinitriles for the preparation of diamines

Info

Publication number: CN105658617A
Application number: CN201480050300.9A
Authority: CN
Inventors: 增·H·赵勋; 斯图尔特·福赛思; 托马斯·A·米茨卡; 迈克尔·C·奎因三世; 约翰·J·奥斯特麦尔; 道格拉斯·J·里斯特勒; 费尔迪·J·托泽
Original assignee: Invista Technologies SARL Switzerland
Current assignee: Invista Technologies SARL Switzerland
Priority date: 2013-09-13
Filing date: 2014-09-10
Publication date: 2016-06-08
Also published as: TW201514131A; WO2015038678A1

Abstract

Disclosed is a method for hydrogenating a dinitrile to form a diamine. Also disclosed is a method for preparing a catalyst for this hydrogenation reaction by reducing iron oxide with hydrogen. The catalyst ages during the course of making the diamine. An aged catalyst is partially reactivated by interrupting the flow of dinitrile and ammonia feed to a reactor, while maintaining a flow of hydrogen to the reactor.

Description

Make dinitrile hydrogenation to prepare diamines

Technical field

This disclosure relates to a kind of method for the preparation of catalyzer and relates to the effective method for hydrogenation of described catalyzer. More properly say, the present invention relates to catalytic hydrogenation organic nitrile under heterogeneous iron catalyst exists. It is hexamethylene-diamine and methyl cellosolve acetate glutaronitrile (especially 2-methyl cellosolve acetate glutaronitrile) hydrogenation is 2-methyl pentamethylene diamine that the example of this kind of reaction comprises adiponitrile hydrogenation.

Background technology

It is known by the method that the hydrogenation of compounds comprising itrile group is amine. Dinitrile hydrogenation is corresponding diamines is a kind of method having employed a very long time, and especially adiponitrile hydrogenation is hexamethylene-diamine, and hexamethylene-diamine prepares nylon-6, the basic material of 6.

In recent years, the concern that aliphatics dinitrile hydrogenation (sometimes also referred to as semihydrogenation) is amino-nitrile day by day being increased, especially adiponitrile hydrogenation is ACN, thus directly obtains or obtain nylon-6 via hexanolactam.

The United States Patent (USP) of the people such as Ziemecki the 5th, 151, No. 543 disclose a kind of is the method for corresponding amino-nitrile by aliphatics dintrile selective hydration, described method is at 25-150 DEG C and under the pressure being greater than normal atmosphere, under existing relative to the solvent of dintrile at least 2/1 molar excess (described solvent comprises the liquefied ammonia or alcohol with 1 to 4 carbon atoms and the mineral alkali dissolved in described alcohol), under Reni catalyst (Raneycatalyst) exists, gained amino-nitrile reclaims as primary product.

The United States Patent (USP) of the people such as Kershaw the 3rd, 696, No. 153 disclose a kind of method of catalytic hydrogenation adiponitrile under the catalyzer of a granular form derived from iron cpd (such as ferric oxide) exists, and described catalyzer is being no more than at the temperature of 600 DEG C to use Hydrogen activation.

The United States Patent (USP) of the people such as Bivens the 3rd, 758, No. 584 disclose a kind of is the method for hexamethylene-diamine by adiponitrile catalytic hydrogenation under the catalyzer derived from cobalt or iron cpd (such as ferric oxide) exists, and described catalyzer activates under about 300 DEG C to the temperature within the scope of about 600 DEG C in the mixture of hydrogen with ammonia.

For making the catalyzer of dinitrile hydrogenation formation diamines aging in time. Along with catalyst aging, the active reduction of catalyzer. Aging selectivity also being caused to lose, selectivity loses the by product causing producing not need. For example, when adiponitrile hydrogenation forms hexamethylene-diamine, it is not necessary to by product can comprise two (hexa-methylene) triamine, diamino-cyclohexane and hexamethylene imine.

In order to compensate due to aging caused loss of activity, it is possible to improve the temperature of dintrile and hydrogen reaction. The temperature in that this temperature improves the reactant that can enter one or more reactor by improving is implemented.Described reaction is thermopositive reaction. Therefore, temperature from the effluent of one or more reactor will exceed the temperature of the charging of these reactors.

There is the upper limit in the temperature of the effluent carrying out autoreactor. Specifically, the catalyst particle in catalyst fixed bed often sinters at up to the temperature of 190 DEG C. The sintering of catalyst particle causes catalyst surface area to lose. Therefore, usually close one or more reactor when temperature of reaction must be improved, thus reach the upper limit of the temperature of reactor effluent.

The problem closing reactor is specifying reaction cycle or the product that can produce between active period to become few. Another problem closing reactor due to catalyst aging is must more catalyst changeout. The number of times that catalyzer must be changed is more many, owing to catalyzer cost increases, so whole method is more expensive. In addition because catalyzer can spontaneous combustion, so more catalyst changeout especially has problems. Therefore, every time more catalyst changeout time, at process raw catalyst with dispose and relate to cost in aging catalyst. The disposal of aging catalyst can relate in inert atmosphere by catalyst transport to catalyst deactivation unit, and in described catalyst deactivation unit, catalyzer is by slow oxidation.

Summary of the invention

In view of the problem relevant with catalyst aging, it is necessary to the life-span of extending catalyst. Embodiment disclosed by this paper, by least part of for aging catalyst reactivate on the spot. This kind of reactivate relates to the dintrile incoming flow that brief interruption leads to one or more reactor. Hydrogen stream is maintained during this interruption. Unexpectedly, such brief interruption dintrile incoming flow causes at least part of reactivate of catalyzer.

Diamines is obtained by dintrile being changed into the method for diamines. Described method can comprise following step:

A the charging comprising dintrile, liquid state or supercritical ammine and hydrogen is introduced at least one and is comprised in catalyst fixed bed convertor by () continuously;

B () maintains the condition in each convertor of step (a) so that dintrile and hydrogen reaction form diamines;

C () makes the effluent comprising diamines exit from each convertor;

D temperature that () improves the charging leading at least one convertor in time is to maintain enough level of conversion and compensate for catalyst is aging;

E () interrupts entering dintrile and the ammonia incoming flow of at least one convertor, maintain the hydrogen stream entering described convertor simultaneously;

F () flushes out remaining dintrile charging, ammonia and diamines product from the convertor of step (e), maintain hydrogen stream through described convertor simultaneously; And

G () recovers to enter the ammonia of convertor and the outflow logistics of dintrile incoming flow and the convertor from step (e) of step (f).

Manufacture level after step (g) can be in the manufacture level similar before with step (d), maintains the temperature of temperature lower than the described charging before step (e) of the charging leading to described convertor simultaneously. The similar manufacture level of step (g) can manufacture level before step (e) 10% within, such as, within 5%, such as, within 2%, such as identical with the manufacture level before step (e).

Each convertor can comprise the cylinder-shaped sleeve being filled with catalyst fixed bed vertical arrangement. The bottom of cylinder-shaped sleeve can comprise at least two outlet openings further. The top of cylinder-shaped sleeve can comprise the void space being placed in catalyst fixed bed top. By the charging comprising dintrile, liquid state or supercritical ammine and hydrogen is introduced in the void space above catalyst bed, charging is made to be downward through catalyst bed and effluent is exited via the outlet opening of sleeve bottom, it is possible to charging to be introduced in each convertor and effluent can exit from each convertor.

Each convertor can comprise the vertical tube of vertically arrangement further, and it extends up through the center bottom cylinder-shaped sleeve, through stagnant catalyst bed and extend in cylinder-shaped sleeve the void space of the level attitude higher than stagnant catalyst bed. Vertical tube can be included in the entrance bottom cylinder-shaped sleeve and at least one outlet in the void space region of sleeve pipe. By the following method, it is possible to charging introduced in each convertor and effluent can exit from each convertor, described method comprises following step:

I the charging comprising dintrile, liquid state or supercritical ammine and hydrogen is introduced in the entrance of vertical tube by ();

(ii) charging is made upwards to flow through the outlet of vertical tube to vertical tube;

(iii) charging is made to flow downwards through the catalyst bed in the annular space between vertical tube and the vertical wall of sleeve pipe; And

(iv) effluent is made to exit via the outlet opening in sleeve bottom.

Dintrile can be converted into diamines in the convertor that at least three are connected in series. Effluent from the first convertor in described series is passed to the 2nd convertor in described series, and the effluent from the 2nd convertor in described series is passed to the 3rd convertor in described series. During dintrile is converted into diamines, the effluent from the first convertor is cooled, passes to the 2nd convertor subsequently, and the effluent from the 2nd convertor is cooled, pass to the 3rd convertor subsequently. The part reactivate of catalyzer can be undertaken by interrupting leading to the dintrile incoming flow of all reactors being connected in series.

In step (b), under the pressure in each convertor can maintain the level of at least 4000psig (27,680kPa). Catalyzer can be the ferric oxide of reduction form. Dintrile can be adiponitrile (ADN) and diamines can be hexamethylene-diamine (HMD). Dintrile can be methyl cellosolve acetate glutaronitrile (MGN) and diamines can be 2-methyl pentamethylene diamine (MPMD).

The temperature in of at least one convertor can be monitored in time. When this temperature in is increased to predeterminated level in step (d) period, it is possible to initial step (e).

The temperature out of at least one convertor can be monitored in time. When this temperature out is increased to predeterminated level in step (d) period, it is possible to initial step (e).

The manufacture level of hexamethylene imine (HMI) can be monitored in time. When the manufacture level of this hexamethylene imine (HMI) is increased to predeterminated level in step (d) period, it is possible to initial step (e).

The manufacture level of the hexamethylene imine (HMI) after step (e) can be less than the manufacture level of the hexamethylene imine before step (e) starts (HMI).

Accompanying drawing explanation

Fig. 1 is that displaying makes the graphic of four stage method for transformation of dinitrile hydrogenation generation diamines.

Fig. 2 shows graphic for the catalyst activation system by preparing catalyzer with hydrogen reducing ferric oxide.

Fig. 3 is the graphic of the details of the ammonia recovery system of displaying shown in Fig. 1.

Fig. 4 shows for making the reaction under liquefied ammonia exists of adiponitrile and hydrogen form the first part of the reaction section of hexamethylene-diamine.

Fig. 5 shows for making the reaction under liquefied ammonia exists of adiponitrile and hydrogen form the second section of the reaction section of hexamethylene-diamine.

Fig. 6 shows the first part of the recovery section of the component of the product stream produced for reclaiming in the reaction section of Fig. 4 and 5.

Fig. 7 shows the second section of the recovery section of the component of the product stream produced for reclaiming in the reaction section of Fig. 4 and 5.

Fig. 8 A shows the first example for the refining section obtaining refining dintrile product.

Fig. 8 B and 8C shows the example of the distillation section shown in Fig. 8 A.

Fig. 9 shows the 2nd example for the refining section obtaining refining dintrile product.

Figure 10 is the plan view of catalyzer cylinder.

Figure 11 is the side-view of catalyzer cylinder.

Figure 12 is the sectional view of catalyzer cylinder along line 3-3 of Fig. 2.

Figure 13 A is the plan view of convertor.

Figure 13 B is the decomposition view of convertor.

Figure 14 A is the side-view of convertor.

Figure 14 B is the sectional view of convertor along line 2B-2B of Figure 14 A.

Figure 15 is the plan view of the lockout mechanism of convertor.

Figure 16 is the cross sectional view of the encloses container with lockout mechanism.

Embodiment

Unless in addition clearly definition or statement or unless the other clear stipulaties of context herein, otherwise each following term " (a) " write with odd number grammatical form as used in this article, " one (an) " and " described " can also refer to and contain a plurality of described entity or object. For example, phrase as used in this article " device ", " subassembly ", " mechanism ", " assembly " and " element " can also refer to respectively and contain plural devices, a plurality of subassembly, plurality of mechanisms, plurality of element and a plurality of element.

As used herein, each following term " comprising (includes) ", " comprising (including) ", " having (has) ", " having (having) ", " comprising (comprises) " and " comprising (comprising) " and its language or grammatical variants, derivative and/or cognate mean " including, but is not limited to ".

In whole explanation description, example and following claims, the numerical value of parameter, feature, object or size can the statement of numerical range form or description. Should fully understanding, described numerical range form provides in order to the embodiment of form presently disclosed is described, and should not be construed as or be considered as the scope of rigid restriction form presently disclosed.

In addition, about statement or description numerical range, phrase " in the scope between the about first numerical value with the about the 2nd numerical value " be considered as equivalence in phrase " in from the about first numerical value to the scope of the about the 2nd numerical value " and identical with described phrase implication, therefore, and the phrase of two implication equivalences can exchange use.

Should be appreciated that, unless special statement in addition herein, otherwise various forms presently disclosed are not limited to following explanation in its application to be described, the details of the operation of the method form set forth in accompanying drawing and example or the order of the step implemented or program and sub-step or sub-routine or order and quantity, or it is not limited to system, system subelement, device, subassembly, sub-assemblies, mechanism, structure, assembly, the peripheral equipment of element and configuration and system form, public utility, the type of accessory and material, composition, structure, arrangement, the details of order and quantity. device, system and method presently disclosed can according to other alternative forms various and with other alternative various practice or enforcement.

It will be further understood that unless in addition clearly definition or statement herein, otherwise in this disclosure in the whole text, all technology used herein and scientific words, term and/or phrase have usual the understood same or similar implication with the those of ordinary skill of this area. In this disclosure in the whole text, word used herein, term and note method are for purposes of illustration and should not be regarded as limiting.

Abbreviation and definition

Use following abbreviation and definition herein:

Unless otherwise indicated, otherwise ADN=adiponitrile; AMC=6-aminocapronitrile; Two (hexa-methylene) triamine of BHMT=; DCH=diamino-cyclohexane; ESN=ethyl succinonitrile; HMI=hexamethylene imine; MCPD=methyl ring pentamethylene diamine; MGN=2-methyl cellosolve acetate glutaronitrile; 3-MPIP=3-methyl piperidine; MPMD=2-methyl pentamethylene diamine; The organic compound of organic dinitriles=comprise two itrile groups, such as ADN; Ppm=is in the hundred of weight rates very much. When comparing two levels, term " similar level " means two levels and differs each other within 10%, such as, within 5%, such as, within 2%. When comparing two temperature of reaction, term " lesser temps " means difference 5 degrees Celsius, 10 degrees Celsius, 15 degrees Celsius, 20 degrees Celsius or more.

The detailed description of Fig. 1

The general flow that dintrile is converted into diamines via a certain system by reactant and product can be described with reference to Figure 1. Fig. 1 is that displaying makes the graphic of four stage method for transformation of dinitrile hydrogenation generation diamines.

In FIG, ammonia source enters ammonia pump 10 through pipeline 2. Sources of hydrogen also enters hydrogen gas compressor 14 through pipeline 4. Ammonia enters pipeline 18 from ammonia pump 10 through pipeline 12, and hydrogen enters pipeline 18 from hydrogen gas compressor 14 through pipeline 16. Ammonia and hydrogen in pipeline 18 carry out part heating in heat exchanger 20, and then it is through pipeline 22 to convertor preheater 24. The ammonia through heating and hydrogen from preheater 24 pass a series of four convertors subsequently, are depicted as convertor 42,44,46 and 48 in FIG.

By dintrile feed source from pipeline 28 feed-in dintrile pump 30. Dintrile charging is from dintrile pump 30 through pipeline 32 to pipeline 34. Part dintrile charging can through pipeline 34 to ammonia feeding line 2. Dintrile by special in the pump of dintrile charging, can also separate introducing with ammonia. Part dintrile charging can also be flowed 36 via side and be passed to pipeline 26 from pipeline 34 to introduce first stage convertor 42. Similarly, the fresh dintrile charging of subordinate phase convertor 44 and phase III convertor 46 is led in side stream 38 and 40 offer. , as depicted in FIG. 1, in addition the fresh dintrile charging in pipeline 34 is introduced in fourth stage convertor 48.

According to embodiment unshowned in Fig. 1, part hydrogen feed can introduce the downstream of first stage convertor 42 and the downstream of optionally subordinate phase reactor 44 and phase III reactor 46. According to another embodiment unshowned in Fig. 1, it is not necessary to fresh dintrile charging is introduced in each convertor. For example, a certain position, first stage convertor 42 upstream can optionally be introduced in all dintrile chargings.

Effluent from first stage convertor 42 arrives subordinate phase convertor 44 through pipeline 50. The outlet position of first stage convertor 42 and via pipeline 38 by the position between the position of fresh dintrile charging introduction pipe line 50, it is possible at least one Fig. 1, unshowned heat exchanger or water cooler cool the effluent from first stage convertor.

From the effluent of subordinate phase convertor 44 through pipeline 52 to phase III convertor 46. The outlet position of subordinate phase convertor 44 and via pipeline 40 by the position between the position of fresh dintrile charging introduction pipe line 52, it is possible at least one Fig. 1, unshowned heat exchanger or water cooler cool the effluent from first stage convertor.

Effluent from phase III convertor 46 arrives heat exchanger 20 through pipeline 54, and in described heat exchanger, the heat from phase III converter effluent passes to the refrigerant charging from pipeline 18.The effluent through cooling from phase III convertor 46 arrives fourth stage convertor 48 through pipeline 56 subsequently. The effluent through cooling from phase III convertor 46 optionally can pass water cooler before passing to fourth stage convertor 48, and described water cooler does not illustrate in FIG.

Effluent from fourth stage convertor 48 arrives heat exchanger 60 through pipeline 58. Effluent through cooling passes pipeline 62 to product separation device 64 from heat exchanger 60 subsequently. There is flash distillation in product separation device 64. The liquid phase comprising diamines from product separation device 64 arrives heat exchanger 60 through pipeline 66. From the gas phase comprising hydrogen and ammonia of product separation device 64 through pipeline 86, to gas circulating compressor 88, to promote, hydrogen and ammonia flow through pipeline 18.

Liquid phase from product separation device 64 heats in heat exchanger 60, through pipeline 68 to ammonia recovery system 70. Ammonia recovery system comprises recovery ammonia tower (not shown in figure 1) and condenser (not shown in figure 1). But, Fig. 3 shows the details of hereafter described ammonia recovery system, described ammonia recovery system comprises recovery ammonia tower and condenser. The crude product comprising diamines is obtained and described crude product leaves ammonia recovery system via pipeline 72 from the bottom of ammonia tower. Gas phase top material from recovery ammonia tower spreads in condenser, in described condenser, is formed and comprises the overhead product phase of ammonia and comprise the steam phase of hydrogen. Part overhead product can return recovery ammonia tower by backflow form mutually. Part overhead product can be transported at least one hold-up vessel mutually and store. Part overhead product can also be recycled to hydrogenation as ammonia charging mutually. In FIG, this kind of recirculation of ammonia is represented to pipeline 2 from ammonia recovery system through pipeline 74 by ammonia.

The steam carrying out condenser in ammonia recovery system 70 is mutually through pipeline 76 to ammonia absorber 78. This steam comprises hydrogen and residual ammonia mutually. Steam by processing with the water washing from pipeline 80 in ammonia absorber 78. Ammoniacal liquor is removed from ammonia absorber via pipeline 82. The steam comprising hydrogen leaves ammonia absorber 78 through pipeline 84 mutually. The hydrogen in streams in pipeline 84 can burning in the combustion unit of such as boiler or combustion tower. From ammonia absorber 78 steam phase at least partially can as hydrogen feed recirculation, its restricted condition for remove water from streams. If water is not removed completely from this streams, so water can make the poisoning of catalyst in convertor.

The steam reclaimed from product separation device 64 comprises hydrogen mutually. This steam can also comprise ammonia mutually. This steam mutually can from product separation device 64 through pipeline 86 to gas circulating compressor 88 so that recirculation enters pipeline 18.

In optional embodiment, pipeline 76 comprises hydrogen and ammonia steam phase at least partially can through the charging of unshowned pipeline in Fig. 1 as catalyst activation unit, described catalyst activation unit is used for by preparing catalyzer with hydrogen reducing ferric oxide.

The detailed description of catalyzer

Catalyzer in described method is applicable to making the hydrogenation catalyst that dinitrile hydrogenation is the mixture of diamines or diamines and amino-nitrile. This kind of catalyzer can comprise group VIII element, comprises iron, cobalt, nickel, rhodium, palladium, ruthenium and its combination. Except group VIII element mentioned above, described catalyzer can also contain one or more promotor, such as one or more group vib elements, such as chromium, molybdenum and tungsten.Described promotor can by the weight of catalyzer with 0.01% to 15%, and the concentration of such as 0.5% to 5% exists. Described catalyzer can also in alloy or indivedual metal or sponge metal catalyst form, and described alloy comprises the sosoloid of two or more metals. " sponge grease " is the metal with the porous " skeleton " that can extend or " sponge sample " structure, it is preferable that substrate metal (such as, iron, cobalt or nickel), and it contains dissolved aluminum, optionally containing promotor. The amount of iron existing in catalyzer, cobalt or nickel can change. The total amount of the iron contained by skeleton catayst, cobalt or the nickel that are applicable in the inventive method be about 30 weight % to about 97 weight % iron, cobalt and/or nickel, such as about 85 weight % to about 97 weight % iron, cobalt or nickel, such as 85%-95% nickel. Sponge catalysts can such as be selected from the metal-modified of the group that is made up of chromium and molybdenum by least one. Sponge metal catalyst can also contain the bubble hydrogen in surface hydration oxide compound, the hydroperoxyl radical adsorbed and hole. Catalyzer of the present invention can also comprise aluminium, and such as about 2 weight % are to 15 weight % aluminium, and such as about 4 weight % are to 10 weight % aluminium. Commercially available sponge type catalyst be can from the GraceChemicalCo. of Maryland State Colombia obtain through promote or do not promoteNi orPromotor. The catalyzer comprising group VIII metal is described in No. 6,376,714th, United States Patent (USP).

Described catalyzer can have carrier or carrier free.

Can by preparing catalyzer with the oxide compound of hydrogen reducing group VIII metal. , it is possible to by more than 200 DEG C but under being no more than the temperature of 600 DEG C, being heated by ferric oxide in presence of hydrogen, for example iron oxide reduction at least partially is made to be that metallic iron carrys out deactivated catalyst. Can continue to activate until in iron available oxygen at least 80 weight % oneself be removed, and activation can be continued until all (such as 95% to 98%) available oxygen is removed substantially. During activating, it is necessary to prevent the water vapour back diffusion formed. The example of catalyst activation technology is described in No. 3,986,985th, United States Patent (USP).

Can carrying out on the spot for dintrile is converted in the reactor of diamines one or more at least partially of catalyst activation. For example, referring to Fig. 1, it is possible to load ferric oxide catalyst presoma in reactor 42,44,46 and 48. Hydrogen can pass through on catalyst precursor when being enough to reducing iron oxides subsequently. When reaching enough catalyst activation degree, it is possible to charging comprise dintrile and reactor can be maintained be enough to dintrile is converted into diamines when.

Catalyst activation can occur in catalyst activation district at least partially, described catalyst activation district with separate for dintrile being converted into the reactor of diamines. The example in this kind of independent catalyst activation district is described with reference to figure 2 herein, and it is discussed hereinafter more in detail. When catalyst precursor reaches enough activation degrees, it is possible to transferred to one or more for dintrile is converted in the reactor of diamines.

From catalyst activation district, activated catalyzer is transferred to independent reactor may have problems. For example, through reduction ferric oxide catalyst normally can spontaneous combustion and must protected not affect by aerial oxygen. According to an embodiment, activated catalyzer from catalyst activation district can cover with rare gas element (such as nitrogen), and maintains in inert atmosphere until activated catalyzer is loaded onto one or more for being converted in the reactor of diamines by dintrile.In another embodiment, activated catalyzer can carry out part passivation transferring to before being converted in the reaction zone of diamines by dintrile. This kind of passivation can by making source of oxygen by occurring above the activated catalyzer in region of activation before transfer catalyst. This kind of passivation makes the outside surface of catalyst particle be oxidized at least in part again, and catalyzer by catalyst particle inside maintains the state of being reduced simultaneously. Will after catalyst deactivation be loaded in reactor (reactor 42,44,46 and 46 of such as Fig. 1), it is possible to make hydrogen by above catalyst deactivation when the ferric oxide on reducing catalyst particle surface. The example of catalyst deactivation technology is described in No. 6,815,388th, United States Patent (USP).

The applicable presoma of this kind of iron catalyst comprises ferric oxide, ironic hydroxide, Iron oxyhydroxides or its mixture. Example comprises ferric oxide (III), ferric oxide (II, III), ferric oxide (II), ironic hydroxide (II), ironic hydroxide (III) or Iron oxyhydroxides (such as FeOOH). Can use synthesis or naturally occurring ferric oxide, ironic hydroxide or Iron oxyhydroxides, such as magnetite, it has Fe₃O₄Desirable chemical formula; Limonite, it has Fe₂O₃H₂The desirable chemical formula of O; Or red iron ore (rhombohedral iron ore), it has Fe₂O₃Desirable chemical formula. The example being used as the iron oxide source for the presoma manufacturing hydrogenation catalyst is described in No. 6,815,388th, United States Patent (USP).

The example of ferric oxide presoma is Sweden's magnetite (Swedishmagnetite). The composition of this kind of magnetite can measure easily through the ICP analysis of spectral method using skilled practitioner to be familiar with. It is one or more that ferric oxide catalyst presoma can comprise in the group being selected from and being made up of following presoma: total iron content is greater than 65 weight %, Fe (II) and Fe (III) ratio are between about 0.60 to about 0.75, total Mg content is greater than 800ppm be weight to being less than 6000ppm, total aluminium content is greater than about 700ppm be weight to being less than 2500ppm, total sodium content is less than about 400ppm be weight, total potassium content is less than about 400ppm be weight, and the size-grade distribution within the scope of 1.0 to 2.5 millimeters is greater than about 90%. Ferric oxide catalyst presoma similar substantially is described in the United States Patent (USP) No. 4,064,172 and No. 3,986,985 of the people such as Dewdney.

The reactor 42,44,46 and 48 of Fig. 1 can be the reactor of fixed-bed reactor or other type. The example of the reactor of fixed bed is not used to be the United States Patent (USP) the 6th of the people such as the U.S. such as people such as Zhang openly applies for 2011/0165029, Benham, the United States Patent (USP) 8,236 of the people such as No. 068,760 and Hou, described in 007, there is the slurry bubble column reactor of riser pipe and downtake. Slurry bubble column reactor easily can be removed reaction heat and provide isothermal operation substantially.

Fixed-bed reactor can have and comprise catalyst fixed bed barrel. Catalyzer cylinder can be moveable. Specifically, moveable barrel may can load catalyst precursor (such as ferric oxide) and be placed in catalyst activation unit. Catalyst precursor in catalyzer cylinder can be activated subsequently in catalyst activation unit. The barrel comprising activated catalyzer can move in reactor 42,44,46 and 48 subsequently one or more in. After the reaction closed in reactor 42,44,46 and 48, then can move discharge barrel from one or more reactor and be transported to catalyst deactivation unit.When barrel is transported to reactor from catalyst activation unit maybe when barrel is transported to catalyst deactivation unit from reactor, the catalyzer in barrel can cover in rare gas element (such as nitrogen).

Deactivating of auto-ignitable catalyst in barrel can by making oxygen-containing gas be undertaken by catalyzer cylinder with control mode. This deactivates and can carry out in catalyst deactivation unit.

The detailed description of Fig. 2

Reactant and product can be described with reference to Figure 2 through the general flow of the ferric oxide catalyst of reduction via the preparation of a certain system. Fig. 2 shows graphic for the catalyst activation system by preparing catalyzer with hydrogen reducing ferric oxide.

In fig. 2, the first sources of hydrogen 100 and the 2nd sources of hydrogen 104 is depicted. However, it should be appreciated that hydrogen can from single source or the supply of two or more source. Hydrogen from the first source 100 passes through pipeline 102, and/or advances to common hydrogen supply line 108 from the hydrogen in the 2nd source 104 through pipeline 106. In an embodiment, the first sources of hydrogen 100 comprises in pipeline 76 the steam phase left from the ammonia recovery system 70 shown in Fig. 1 at least partially. In another embodiment, the 2nd sources of hydrogen 104 comprises the hydrogen from Hydrogen Line. When using Hydrogen Line, hydrogen such as can carry out purifying by transformation adsorption treatment. When use two sources of hydrogen, it can use simultaneously, or uses by stopping the flowing interval of the hydrogen from the first source 100 when using the 2nd source 104, and vice versa.

By the hydrogen feed feed-in preheater 110 in pipeline 108, and the hydrogen through heating is made to arrive hydrogen/ammonia mixing tank 118 through pipeline 112. The ammonia charging leading to hydrogen/ammonia mixing tank 118 derives from ammonia source 114. Ammonia charging enters hydrogen/ammonia mixing tank 118 via pipeline 116. Hydrogen/ammonia charging through mixing enters heat exchanger 124 with to be heated through pipeline 120 and pipeline 122. Hydrogen/ammonia charging through heating passes pipeline 126 subsequently to preheater 128 to be heated to the temperature of applicable reducing iron oxides further. This hydrogen/ammonia charging subsequently through pipeline 130 to catalyst activation unit 132 so that reducing iron oxides. In catalyst activation unit 132, ferric oxide is reduced, and a part of hydrogen in charging is converted into water (H₂O) and a part ammonia (NH₃) it is decomposed to form nitrogen (N₂) and hydrogen (H₂)��

From the effluent of catalyst activation unit 132 through pipeline 134 to heat exchanger 124, in described heat exchanger, the hydrogen that the heat from effluent is transferred in pipeline 122/ammonia charging and effluent are cooled. Effluent through cooling passes pipeline 136 subsequently to water cooler 138 to cool further. Water cooler 138 can utilize refrigeration carry out all or partly cool to make the maximum water vapor condensation in pipeline 136. Entering separator 142 from the effluent of water cooler 138 through pipeline 140, described effluent comprises the liquid phase comprising ammonia and water and comprises the gas phase of hydrogen, ammonia and nitrogen. Liquid phase is from separator 142 through pipeline 148 and may be directed to hold-up vessel, and described hold-up vessel does not illustrate in fig. 2.

From the passing to compressor 146 by pipeline 144 at least partially and enter pipeline 122 to be recycled to catalyst activation unit 132 of gas phase of separator 142. Minimum in order to make the accumulation of the nitrogen in recirculation loop drop to, it is also possible to obtain part gas phase as purification stream via pipeline 150 from separator 142.

According to optional embodiment unshowned in Fig. 2, do not use preheater 110 and hydrogen/ammonia mixing tank 118. In the embodiment that this is optional, from the ammonia in ammonia source directly from pipeline 120 feedthrough system, it does not have first mix with hydrogen. In addition, from the direct feed-in water cooler 138 of hydrogen in source 100 or source 104, it does not have first mix with ammonia.

The detailed description of Fig. 3

Fig. 3 is the graphic of the details of the ammonia recovery system 70 of displaying shown in Fig. 1. In figure 3, by, in the streams 68 feed-in recovery ammonia tower 200 of heating, the described streams through heating also show in FIG and comprises ammonia, hydrogen and diamines. Diamines product stream 206 enters hold-up vessel 210 from the bottom of recovery ammonia tower 200. Crude product in hold-up vessel 210 can be refined further, such as, by step illustrated in Fig. 8 A and 9. Headpiece stream 202 comprises hydrogen and ammonia steam, enters condenser 220. Part ammonia condensing liquid enters recovery ammonia tower 200 through pipeline 204 as reflux. Another part ammonia condensing liquid enters hold-up vessel 230 from condenser 220 through pipeline 212. A part of ammonia condensing liquid in hold-up vessel 230 can be recycled in pipeline 2 through pipeline 74, as the ammonia charging of dintrile conversion process as shown in Figure 1.

Steam flow enters ammonia absorber 78 from condenser 220 through pipeline 214. A part for this steam flow can enter pipeline 76 from pipeline 214 to be used as the hydrogen feed stream as described in the catalyst activation system as shown in about Fig. 2 as side stream.

Current are introduced in ammonia absorber 78 through pipeline 80. Ammonia aqua stream 82 from ammonia absorber 78 by entering hold-up vessel 240. The steam flow comprising hydrogen leaves ammonia absorber 78 through pipeline 84. Anhydrous ammonia can be reclaimed from the ammoniacal liquor hold-up vessel 240 by distillation and make it be recycled to dinitrile hydrogenation technique with ammonia charging form.

The general introduction of Fig. 4 to 7

Fig. 4 shows a kind of method making adiponitrile and hydrogen reaction formation hexamethylene-diamine under liquefied ammonia exists to 7. Fig. 4 and 5 shows the reaction section of this reaction. Fig. 4 shows and feed component is merged in reaction section and be heated to the part of temperature of reaction. Fig. 5 shows that in reaction section, the part of reaction occurs feed component. Fig. 6 and 7 shows the recovery section of the component of the product stream produced for reclaiming in the reaction section of Fig. 4 and 5. Fig. 6 shows the part reclaiming rough hexamethylene-diamine product and unreacted hydrogen in recovery section. Fig. 7 shows the part reclaiming ammonia in recovery section.

The summary of Fig. 4 and 5

In figures 4 and 5, fresh adiponitrile charging is introduced in reaction section via pipeline 301, and fresh hydrogen charging is introduced in reaction section via pipeline 309, and fresh liquefied ammonia charging is introduced in reaction section via pipeline 313. These chargings and various recirculation feed combinations and through pipeline 308 to conservation type heat exchanger 318 and preheater 323. Charging through heating enters series reaction device 327,337 and 348 through pipeline 326 subsequently. Described reaction is thermopositive reaction. Heat regenerator 329,339 and 350 and water cooler 334,345 and 355 remove in reactor 327,337 and 348 heat produced. A withdrawer and water cooler are arranged in the downstream of each of reactor 327,337 and 348.

Product from reaction section arrives the recovery section shown in Fig. 6 and 7 through pipeline 356.

Refrigerant for heat regenerator 329,339 and 350 passes to reaction section from recovery section via pipeline 332.Refrigerant is the liquid stream from recovery section. Described liquid stream comprises liquefied ammonia and hexamethylene-diamine. This refrigerant enters in each in heat regenerator 329,339 and 350, is formed and comprises the steam flow of ammonia and comprise the liquid stream of ammonia and hexamethylene-diamine. Steam flow returns in recovery section through pipeline 331 and liquid stream returns in recovery section through pipeline 333.

The detailed description of Fig. 4 and 5

Adiponitrile is introduced in reaction section through pipeline 301. Streams at least partially in pipeline 301 can pass in adiponitrile pump 306 and enter pipeline 307 subsequently so that in introduction pipe line 308. Streams in pipeline 308 comprises adiponitrile, hydrogen and liquefied ammonia. Adiponitrile pump 306 can be reciprocating plunger pump or stage chamber pump. Adiponitrile charging can be diverted in pipeline 302 at least partially. Adiponitrile in pipeline 302 passes in recovery section illustrated in Fig. 6 and 7. Specifically, this part of charging pass to pump 303 and subsequently through pipeline 304 and enter subsequently in the adiponitrile resorber 361 of (but not illustrating in Fig. 4 or 5) shown in Fig. 6. Adiponitrile stream from the bottom of adiponitrile resorber 361 comprises adiponitrile and ammonia. The streams comprising adiponitrile and ammonia returns reaction section via pipeline 305 and introduces in adiponitrile incoming flow along pipeline 301.

Fresh hydrogen charging is introduced in reaction section via pipeline 309. Hydrogen feed can pass in compression section 311 and enter pipeline 312 and enter pipeline 308 subsequently to introduce in convertor 327,337 and 348 at least partially. Compression section 311 can comprise such as two four stage hydrogen gas compressors. At least one recycle hydrogen air-flow can also be illustrated from Fig. 6 and 7 recovery section pass in the pipeline 309 of reaction section. For example, hydrogen from adiponitrile resorber 361 can through pipeline 310 to pipeline 309. Fresh feed through combination and the hydrogen feed through recirculation pass to pipeline 312 through compression section 311 and enter pipeline 308 subsequently. Can also by the streamed acquisition hydrogen recirculation flow of top material from high-pressure separator 357, it to gas circulating compressor 317 and enters pipeline 308 through pipeline 316 subsequently.

Fresh liquefied ammonia charging enters ammonia pump 314 through pipeline 313 and to pipeline 315 and enters pipeline 308 subsequently. Ammonia pump 314 can be reciprocating plunger pump or stage chamber pump. Some adiponitriles may be directed to ammonia pump to help flow control and the lubrication of pump assembly.

The charging comprising adiponitrile, hydrogen and liquefied ammonia is passed in conservation type heat exchanger 318 through pipeline 308. This part of charging is by heating in conservation type heat exchanger 318 from the liquid heat stream of reaction section or recovery section. This part of liquid stream is introduced in conservation type heat exchanger 318 through pipeline 319. The example of liquid process stream is the liquid stream from the tower for separating of hexamethylene-diamine and low-boiling compound. This kind of streams is described with streams 463 with reference to figure 8A.

Conservation type heat exchanger 318 can be shell pipe type heat exchanger. Heating fluid can enter conservation type heat exchanger 318 through pipeline 319 and pass the shroud segment of shell pipe type heat exchanger. Reaction-ure fluid to be heated can enter conservation type heat exchanger 318 through pipeline 308 and pass the pipeline section of shell pipe type heat exchanger. The hot-fluid that adds through cooling returns reaction or recovery section through pipeline 320.

Reaction logistics through heating passes to preheater 323 from conservation type heat exchanger 318 through pipeline 321 subsequently.Streams at least partially in pipeline 308 can shunt from conservation type heat exchanger 318 and via pipeline 322 introduction pipe line 321. The amount walking around the streams of conservation type heat exchanger 318 shunting in pipeline 322 may be used for the temperature of the streams controlled in pipeline 321 in feed-in preheater 323.

In order to the streams heated in pipeline 321, in preheater 323, introduce steam via pipeline 324. Steam and/or phlegma through cooling reclaim via pipeline 325.

Reaction logistics through heating enters the first reactor or convertor 327 through pipeline 326 subsequently.

The effluent carrying out autoreactor 327 passes to heat regenerator 329 through pipeline 328. Refrigerant stream comprises hexamethylene-diamine and anhydrous liquid ammonia, passes in heat regenerator 329 via pipeline 332. A part of liquid ammonia vaporization in heat regenerator 329, in refrigerant stream. The streams comprising vaporous ammonia exits from heat regenerator 329 via pipeline 331. The streams comprising hexamethylene-diamine, liquefied ammonia and dissolved hydrogen exits from heat regenerator 329 via pipeline 333.

That carrys out autoreactor 327 passes pipeline 330 through cooling flow effluent stream from heat regenerator 329. Streams at least partially in pipeline 330 passes in water cooler 334. Water cooler 334 can be air-cooler or watercooler. A part of streams in pipeline 330 can also walk around water cooler 334 by being diverted in pipeline 336. By control pipeline 330 is walked around the amount of the streams of water cooler 334, it is possible to control enters the temperature of the streams in reactor 337. All the 2nd reactor 337 is entered via pipeline 335 by the charging of water cooler 334 and any charging walking around water cooler 334.

Although not illustrating in Fig. 5, but a part of streams in pipeline 328 via pipeline unshowned in Fig. 5, can walk around withdrawer 329 and water cooler 334 in the way of controlling to lead to the temperature of the charging of convertor 337.

Although Fig. 5 does not illustrate, but can optionally by direct for the additional feed comprising hydrogen and/or adiponitrile feed-in reactor 337 or by introducing in such as pipeline 330,335 or 336 in indirect feed-in reactor 337.

The effluent carrying out autoreactor 337 passes to heat regenerator 339 through pipeline 338. Refrigerant stream comprises hexamethylene-diamine and anhydrous liquid ammonia, passes in heat regenerator 339 via pipeline 341. Pipeline 341 is the side stream of pipeline 332. A part of liquid ammonia vaporization in heat regenerator 339, in refrigerant stream. The streams comprising vaporous ammonia exits from heat regenerator 339 via pipeline 342 and enters pipeline 331. The streams comprising hexamethylene-diamine and liquefied ammonia is withdrawn into pipeline 344 via pipeline 343 from heat regenerator 339 and enters pipeline 333 subsequently.

That carrys out autoreactor 337 passes pipeline 340 through cooling flow effluent stream from heat regenerator 339. Streams at least partially in pipeline 340 passes in water cooler 345. Water cooler 345 can be air-cooler or watercooler. A part of streams in pipeline 340 can also walk around water cooler 345 by being diverted in pipeline 347. By control pipeline 340 is walked around the amount of the streams of water cooler 345, it is possible to control enters the temperature of the streams in reactor 348. All the 3rd reactor 348 is entered via pipeline 346 by the charging of water cooler 345 and any charging walking around water cooler 345.

Although not illustrating in Fig. 5, but a part of streams in pipeline 338 via pipeline unshowned in Fig. 5, can walk around withdrawer 339 and water cooler 345 in the way of controlling to lead to the temperature of the charging of convertor 348.

Although Fig. 5 does not illustrate, but can optionally by direct for the additional feed comprising hydrogen and/or adiponitrile feed-in reactor 348 or by introducing in such as pipeline 340,346 or 347 in indirect feed-in reactor 348.

The effluent carrying out autoreactor 348 passes to heat regenerator 350 through pipeline 349. Refrigerant stream comprises hexamethylene-diamine and anhydrous liquid ammonia, passes in heat regenerator 350 via pipeline 352. Pipeline 352 is the side stream of pipeline 332. A part of liquid ammonia vaporization in heat regenerator 350, in refrigerant stream. The streams comprising vaporous ammonia exits from heat regenerator 350 via pipeline 354 and enters in pipeline 331. The streams comprising hexamethylene-diamine, liquefied ammonia and dissolved hydrogen is withdrawn into pipeline 344 via pipeline 353 from heat regenerator 350 and enters subsequently in pipeline 333.

That carrys out autoreactor 348 passes pipeline 351 through cooling flow effluent stream from heat regenerator 350. Streams at least partially in pipeline 351 passes in water cooler 355. Water cooler 355 can be air-cooler or watercooler. From the 3rd reactor 348 through cooling flow effluent from water cooler 355 through pipeline 356 to the recovery section shown in Fig. 6 and 7.

Heat regenerator 329,339 and 350 can be the shell pipe type device being similar to shell-and-tube exchanger separately. Effluent from convertor 327,337 and 348 can enter the pipe side of withdrawer, and cooling fluid can enter the shell side of withdrawer. The steam produced in heat regenerator shell side can leave withdrawer via the first pipeline, and can leave withdrawer via the 2nd pipeline from the armpit body of heat regenerator shell side.

The summary of Fig. 6 and 7

In recovery section shown in figs. 6 and 7, ammonia is separated with hexamethylene-diamine with hydrogen, obtains rough hexamethylene-diamine product, and it reclaims via pipeline 385. This crude product is also removed containing in ammonia and other impurity, described ammonia and other impurity in figs. 6 and 7 unshowned purification step. But, Fig. 8 A and 9 illustrates the example of these purification step. Recovery section shown in Fig. 6 and 7 also provides the recovery of hydrogen and ammonia. The hydrogen and the ammonia that reclaim can be recycled to the reaction section shown in Fig. 4 and 5.

Enter the most of hydrogen in the streams of recovery section to be removed in high-pressure separator 357 and MP (medium pressure) separator 359 via pipeline 356. Steam flow from high-pressure separator 357 can directly be recycled to conversion section. Steam flow from MP (medium pressure) separator 359 contains hydrogen and some ammonia. Steam flow from MP (medium pressure) separator 359 with liquid adiponitrile washing in adiponitrile resorber 361, can obtain being rich in the steam flow of hydrogen and comprise the liquid stream of adiponitrile and dissolved ammonia. The feed source that these streams can be used as in reaction section.

The liquid obtained from MP (medium pressure) separator 359 is transferred to withdrawer charging separator 364, obtains the liquid stream of ammonia steam flow and part depletion ammonia. Heat regenerator 329,339 and 350 shown in Figure 5 heats the liquid stream from withdrawer charging separator 364. Being transferred to recovery ammonia section from heat regenerator through heating liquids and steam, described recovery ammonia section comprises withdrawer tailings tank 367, steam water cooler 375, flasher 373, primary flash tank 380 and two-stage flash tank 382. With the streamed recovery ammonia product of top material from steam water cooler 375. This part of ammonia product is stored in anhydrous ammonia tank 398.

Rough hexamethylene-diamine product is reclaimed from two-stage flash tank 382 from liquid bottom streams. Overhead vapor stream from two-stage flash tank 382 comprises ammonia steam. In the figure 7, in low-pressure absorber 413, this ammonia steam is reclaimed with the liquid solution of ammoniacal liquor. In low-pressure absorber 413, wash ammonia steam with water to form ammoniacal liquor.

Fig. 7 also illustrates high pressure absorber 399, and it also washes ammonia steam with water to form the liquor of ammoniacal liquor. In the figure 7, the steam flow of ammonia charging from adiponitrile resorber 361 of high pressure absorber 399 is led to. But, it is possible to other ammonia source unshowned in feed-in Fig. 7 in high pressure absorber 399. The example in this kind of source comprises the ammonia steam obtaining steam from MP (medium pressure) separator 359 in pipeline 360 and discharging from ammonia hold-up vessel 398.

By in the ammonia soln feed-in distillation tower 424 from low-pressure absorber 413 and high pressure absorber 399. From distillation tower 424 recovering liquid bottom water flow and its water charging being used as low-pressure absorber 413 and high pressure absorber 399. Anhydrous ammonia is obtained from distillation tower 424 so that vaporous top material is streamed. The phlegma of this headpiece stream is transferred to anhydrous ammonia storage tank 398. Although not illustrating in Fig. 7, but the anhydrous ammonia in ammonia hold-up vessel 398 can as the source of the recycle of ammonia charging in the conversion section shown in Fig. 4 and 5.

The detailed description of Fig. 6 and 7

As shown in Figure 6, the reactor effluent through cooling in pipeline 356 enters in high-pressure separator 357. The headpiece stream comprising hydrogen and ammonia through pipeline 316 and returns the convertor section shown in Fig. 4 and 5. Streams in pipeline 316 is used as recycled hydrogen and ammonia charging.

The bottoms stream comprising hexamethylene-diamine and liquefied ammonia is from high-pressure separator 357 through pipeline 358 to MP (medium pressure) separator 359. The overhead vapor stream comprising ammonia and hydrogen is from MP (medium pressure) separator 359 through pipeline 360 to adiponitrile resorber 361. Adiponitrile is via in pipeline 304 feed-in adiponitrile resorber 361. Gas in adiponitrile washing absorption device 361. Ammonia is dissolved in adiponitrile. The liquid phase comprising adiponitrile and dissolved ammonia is from resorber 361 through pipeline 305. As shown in Figure 4, it may also be useful to the streams in pipeline 305 is as the charging for adiponitrile is converted into hexamethylene-diamine.

Vapor phase feed stream is obtained from resorber 361. Compared to the vapor phase feed stream entering resorber 361 in pipeline 360, this streams is rich in hydrogen and lacks ammonia. This is rich in the recycled hydrogen incoming flow can passed pipeline 310 at least partially and be used as in conversion process of the streams of hydrogen. The pipeline 362 that can also pass at least partially of the streams being rich in hydrogen arrives high pressure absorber 399. Specifically, the streams in pipeline 362 can be the purification stream of the hydrogen stream from adiponitrile resorber 361. The amount of the hydrogen purified by this way can be enough to keep the hydrogen cleaning of about 1% with such as total hydrogen feed rate.

During startup, closedown and normal running, it is possible to optionally walk around adiponitrile resorber 361. During startup, closedown and normal running, it is possible to steam is directed to high pressure absorber 399 from MP (medium pressure) separator 359.

Liquid bottom streams from middle pressure resorber 359 arrives withdrawer charging separator 364 through pipeline 363. In withdrawer charging separator 364, reduce the pressure from the liquid efflunent of MP (medium pressure) separator 359 in pipeline 363, the liquid coolant charging that the vapor feed that obtains being applicable to leading to recovery ammonia section and obtaining is applicable in heat regenerator 329,339 and 350.Overhead vapor stream is from withdrawer charging separator 364 through pipeline 365 to pipeline 368 to introduce steam water cooler 375. Liquid bottom streams is from charging separator 364 through pipeline 332 and enters the heat regenerator shown in Fig. 5 (i.e. heat regenerator 329,339 and 350). Steam flow from heat regenerator arrives steam water cooler 375 through pipeline 331. Liquid stream from heat regenerator arrives withdrawer tailings tank 367 through pipeline 333.

Steam flow is obtained from withdrawer tailings tank 367 and it is through pipeline 368 to steam water cooler 375 so that top material is streamed. Liquid bottom streams is obtained and it is through pipeline 370 to pump 371 and subsequently through pipeline 372 to flasher 373 from withdrawer tailings tank 367. Overhead vapor stream is obtained and it to pipeline 368 and enters steam water cooler 375 subsequently through pipeline 374 from flasher 373.

Liquid condensation water is obtained from steam water cooler 375 and it to pump 377 to pipeline 378 and enters flasher 373 through pipeline 376 with bottoms stream form. Obtaining liquid bottom streams from flasher 373, it is through pipeline 379 to primary flash tank 380. Obtaining liquid bottom streams from primary flash tank 380, it is through pipeline 381 to two-stage flash tank 382. To pump 384 and recovery section is left via pipeline 385 subsequently from the bottoms stream flows of two-stage flash tank 382 through pipeline 383.

Streams in pipeline 385 comprises rough hexamethylene-diamine product, and it is transferred in Fig. 6 unshowned refining section. Crude product in pipeline 385 can comprise such as 90wt% hexamethylene-diamine, 9wt% ammonia and other impurity of 1wt%. Other impurity (namely those impurity) except ammonia can comprise boiling point lower than compound higher than hexamethylene-diamine of the compound of hexamethylene-diamine and boiling point. Boiling point comprises hydrogen, methane, diamino-cyclohexane, hexamethylene imine and water lower than the example of the compound of hexamethylene-diamine. Boiling point comprises ACN, adiponitrile and two (hexa-methylene) triamine higher than the example of the compound of hexamethylene-diamine.

Obtaining vaporous headpiece stream from primary flash tank 380, it is through pipeline 386 to ammonia Pistonless compressor 387 and arrives steam water cooler 375 subsequently. From can the discharging via washer (not illustrating in Fig. 6) at least partially of ammonia of this primary flash tank 380, in described washer, it may also be useful to hexamethylene-diamine (HMD) washes any diamines of the ammonia entrained with of leakage off. Vaporous headpiece stream is from steam water cooler 375 through pipeline 390. This streams along pipeline 390 pass to partially or completely condenser 391 and pass to pipeline 392 subsequently. Fluid in water cooler 391 can be used for from the air of refrigeration unit, water coolant or refrigerated water/glycol stream cools. Streams at least partially in pipeline 392 can be transferred to fine setting separator 394. Streams at least partially in pipeline 392 can also walk around fine setting separator 394 by flowing through pipeline 393 to ammonia receptor 396.

In fine setting separator 394, it is separated. Steam is trapped within the head (i.e. upper area) of fine setting separator 394 mutually, and liquid phase collects in the bottom section of fine setting separator 394. Ammonia steam in fine setting separator 394 can be discharged in high pressure absorber 399, low-pressure absorber 413 or adiponitrile resorber 361. Obtaining liquid phase from the bottom of fine setting separator 394, it is through pipeline 395 to ammonia receptor 396.Optionally, the ammonia steam in ammonia receptor 396 can be discharged via unshowned pipeline in Fig. 6 and is transferred to high pressure absorber 399, low-pressure absorber 413 or adiponitrile resorber 361.

The streams merged from pipeline 393 and pipeline 395 is collected ammonia receptor 396. Streams through merging is subsequently through pipeline 397 to anhydrous ammonia storage tank 398.

Ammonia hold-up vessel 398 is containing anhydrous ammonia, and it reclaims when not contacting with water and form ammoniacal liquor. But, exist various containing ammonia streams so that it is contact to wash steam with water, thus from steam, remove ammonia and produce ammonia soln. Ammoniacal liquor can distill to produce anhydrous ammonia in one or more distilation steps. The anhydrous ammonia produced from the distillation of ammoniacal liquor can be reclaimed and it is merged with anhydrous ammonia collected anhydrous ammonia tank 398.

In the figure 7, ammoniacal liquor is obtained from high pressure absorber 399 with from low-pressure absorber 413. In high pressure absorber 399, water is introduced via pipeline 400. In high pressure absorber 399, ammonia steam is introduced via pipeline 362. Ammonia steam can also be introduced via pipeline unshowned Fig. 7 in high pressure absorber 399 from other source. Steam, the steam from anhydrous ammonia storage tank 398 discharge and the steam from ammoniacal liquor hold-up vessel 409 discharge that the example of ammonia vapor source comprises the steam from fine setting separator 394 discharge, discharges from ammonia receptor.

In high pressure absorber 399, water is contacted in a counter-current configuration with ammonia steam. When ammonia steam is dissolved in the water, produce heat. From high pressure absorber 399, steam flow is obtained via pipeline 401. Steam enters decontaminating separator 402 along pipeline 401. A part of inclusion of decontaminating separator 402 returns high pressure absorber 399 via pipeline 403, and a part of inclusion of decontaminating separator 402 obtains along pipeline 404, as purification stream. Purification stream comprises inflammable gas, such as hydrogen and methane. Inflammable gas can burn in combustion unit, and described combustion unit is such as boiler or combustion tower.

Obtaining ammonia aqua stream from the bottom of high pressure absorber 399, it to pump 406 and enters pipeline 407 through pipeline 405 subsequently. A part of streams in pipeline 407 can return in high pressure absorber 399 via pipeline 408. Streams at least partially in pipeline 407 is also through pipeline 408 to ammoniacal liquor hold-up vessel 409.

As shown in FIG. 7, arrive low-pressure absorber capture tank 411 from the headpiece stream of two-stage flash tank 382 through pipeline 410. Vaporous ammonia streams from low pressure capture tank 411 arrives low-pressure absorber 413 through pipeline 412. Water also passes to low-pressure absorber via pipeline 417.

According to an optional embodiment unshowned in Fig. 6 and 7, the steam at least partially in pipeline 410 may be directed to ammonia Pistonless compressor 387 to be recycled in steam water cooler 375.

The source of the water at least partially being introduced in low-pressure absorber 413 and high pressure absorber 399 can be the bottom distillment from ammonia distillation tower 424. As shown in FIG. 7, enter technique water pot 414 from the liquid bottom streams of tower 424 through pipeline 432. Obtaining current from technique water pot 414, it to pump 416 and enters pipeline 417 through pipeline 415 subsequently. As shown in FIG. 7, a part of current in pipeline 417 using side streamed in pipeline 400 obtain and pass to high pressure absorber 399 as water charging. Another part current continue across pipeline 417 and are introduced in low-pressure absorber 413.Optionally such as can add fresh water or make-up water in technique water pot 414 or to any appropriate position of high pressure absorber 399 or low-pressure absorber 413 upstream.

From the steam of low-pressure absorber 413 through pipeline 418. These steams can comprise hydrogen or methane. These steams can pass to combustion unit along pipeline 418, such as boiler or combustion tower.

Water is introduced in low-pressure absorber 413 via pipeline 417, and ammonia steam is introduced in low-pressure absorber 413 via pipeline 412. Water and ammonia flow through low-pressure absorber 413 in a counter-current configuration. During described technique, water collects ammonia by dissolved ammonia. Ammonia is dissolved in the water and produces heat. The ammonia collected with ammoniacal liquor form is from low-pressure absorber 413 through pipeline 419. Streams in pipeline 419 to pump 420 and enters pipeline 421 through pipeline 419 subsequently. A part of ammoniacal liquor in pipeline 421 can pass pipeline 422 and return in low-pressure absorber 413. Ammoniacal liquor at least partially in pipeline 421 also passes pipeline 422 and enters ammoniacal liquor hold-up vessel 409 subsequently.

Ammoniacal liquor from ammoniacal liquor hold-up vessel 409 arrives distillation tower 424 through pipeline 423. From distillation tower 424, the vaporous headpiece stream comprising anhydrous ammonia is obtained via pipeline 425. Vaporous streams in pipeline 425 enters condenser 426 and enters pipeline 427 subsequently. Streams in pipeline 427 is transferred to condenser tank 428. The liquid carrying out condenser tank 428 through pipeline 429 and enters pump 430. A part of streams from pump 430 can return distillation tower 424 by backflow form. Streams at least partially from pump 430 also arrives anhydrous ammonia storage tank 398 through pipeline 431.

The appropriate position that anhydrous ammonia in anhydrous ammonia storage tank 398 can be recycled in the reaction section shown in Fig. 4 and 5 via pipeline unshowned in Fig. 7.

Although the method described in Fig. 4 to 7 is above describing about manufacturing hexamethylene-diamine from adiponitrile, it is to be appreciated that, in this approach, it is possible to manufacture other diamines from other dintrile. For example, it is possible to replace adiponitrile with methyl cellosolve acetate glutaronitrile and produce 2-methyl pentamethylene diamine, instead of hexamethylene-diamine. When manufacturing the dintrile except hexamethylene-diamine, it is possible to suitably adjusting process condition.

The description of the processing condition in Fig. 4 to 7

The charging heating of a series of convertor 327,337 and 348 will be led to and be pressurized to enough levels. Such as, feeding temperature in pipeline 326 can be at least 75 DEG C.

Ammonia is added to provide heat-dissipating thing, thus control is by the heat of hydrogen with the thermopositive reaction generation of adiponitrile to comprising in the incoming flow of hydrogen and adiponitrile. The ammonia introducing enough amounts in convertor 327,337 and 348 by maintaining, the heat produced during hydrogenation process just can be dissipated. Ammonia is also used for dissolving hydrogen. The hydrogen dissolved be dispersed on catalyst particle and with adiponitrile fusion, thus enhance hydrogenation. Generally thinking, when being dissolved in when hydrogen in liquefied ammonia or supercritical phase ammonia, hydrogen can through the liquid film on catalyst surface, and described night, film can comprise nitrile or amine.

Ammonia further suppress and forms various improper by product in convertor. When adiponitrile hydrogenation forms hexamethylene-diamine, it is not necessary to by product can comprise two (hexa-methylene) triamine, diamino-cyclohexane and hexamethylene imine. When 2-methyl cellosolve acetate glutaronitrile hydrogenation forms methyl pentamethylene diamine, it is not necessary to by product can comprise two (methyl five methylene radical) triamine, methylcyclopentane diamines and 3-methyl piperidine.No. 2009/0048466th, U.S. Patent Application Publication describes and during using ammonia solvent to suppress hydrogenating nitriles, forms by product.

Temperature in control convertor 327,337 and 348 is to prevent the temperature in convertor exceedes the temperature occurring a large amount of catalyst degradation and impurity to be formed. For example, if the temperature of catalyzer becomes too high, so catalyst particle can sinter, and causes catalyst surface area loss and activity and selectivity reduction. Can by the temperature of control from the effluent of each convertor so that the temperature of effluent is no more than 200 DEG C, thus the catalyst degradation that this kind is not needed drops to minimum. For example, if the temperature of catalyzer becomes too high, so impurity formation can become too much, causes process yield loss significantly. Can by the temperature of control from the effluent of each convertor so that the temperature of effluent is no more than 200 DEG C, thus make these impurity reactions not needed drop to minimum. In an embodiment, such as, temperature from the effluent of each convertor is 190 DEG C or lower. In another embodiment, such as, temperature from the effluent of each convertor is 180 DEG C or lower.

In the convertor of Fig. 5, especially the hydrogenation in the first convertor 327 can come initial by introducing incoming flow at the temperature of at least 75 DEG C in each convertor. For example, early stage in described technique, the temperature of 80 DEG C to 90 DEG C can be maintained along pipeline 326 to the temperature of the incoming flow of convertor 327 under, the temperature of 80 DEG C to 90 DEG C can be maintained along pipeline 335 to the temperature of the incoming flow of convertor 337 under, and the temperature of 100 DEG C to 150 DEG C can be maintained along pipeline 346 to the temperature of the incoming flow of convertor 348 under.

Catalyzer occurs aging in time. As the catalyst ages, it is possible to the temperature in improving the charging leading to convertor is with compensate for catalyst loss of activity. Finally, catalyzer will become completely aging, and must interrupt reaction and more catalyst changeout. Catalyst change can the entrance of in multiple convertor or temperature out make to carry out when producing no longer economical when exceeding preset temperature or forming by product owing to temperature increases. For example, when the temperature in of one or more convertor is more than 150 DEG C, or when the temperature out of one or more convertor is more than 190 DEG C, it is possible to close hydrogenation process so that more catalyst changeout.

Introduce in convertor with first time charging start and in response activity process till being continued until more catalyst changeout, the temperature leading to the charging of each convertor can drop in the scope of 75 DEG C to 150 DEG C, and can drop on from the temperature of the effluent of each convertor in the scope of 130 DEG C to 190 DEG C.

The hydrogenation occurred in convertor is thermopositive reaction. Therefore, temperature from the effluent of convertor will exceed the charging leading to convertor. For example, temperature from the effluent of the first convertor 327 can be 160 DEG C to 180 DEG C, temperature from the effluent of the 2nd convertor 337 can be 160 DEG C to 180 DEG C, and can be 150 DEG C to 170 DEG C from the temperature of the effluent of the 3rd convertor 348.

Pressure in each convertor should be enough high anhydrous ammonia to maintain liquid state or supercritical state, under the maximum temperature especially obtained in each convertor. Hydrogen, dintrile reactant and diamines product should dissolve or be otherwise dispersed in whole ammonia mutually in. Pressure in each convertor can be at least 2500psig (31,128kPa), such as 4500psig (34,575kPa), such as 5000psig (34,575kPa).

From the effluent of the 3rd convertor 348 in liquid or types of supercritical fluid, it comprises the hexamethylene-diamine of dissolving, anhydrous ammonia and dissolved hydrogen. This kind of fluid can have at least pressure of 2500psig (31,128kPa) and the temperature of at least 150 DEG C. As shown in Fig. 4,5 and 6, from the hydrogen at least partially in the effluent of convertor 348 first by cooling flow effluent in heat regenerator 350 and water cooler 355 and make the effluent through cooling pass to high-pressure separator 357 and remove subsequently. Effluent can in feed-in high-pressure separator 357 before cool at least 80 DEG C. High-pressure separator 357 can operate when making headpiece stream 316 mainly comprise hydrogen with molar concentration meter. The temperature introducing the charging in high-pressure separator 357 can be less than 70 DEG C, such as 50 DEG C. Pressure in high-pressure separator 357 can be less than 4500psig (31,128kPa), such as 4200psig (29,059kPa).

Liquid bottom streams from high-pressure separator 357 comprises some dissolved hydrogens. Great majority in the dissolved hydrogen of this kind of residual are removed in MP (medium pressure) separator 359. MP (medium pressure) separator 359 can operate under the temperature condition substantially the same with high-pressure separator 357. For example, the temperature introducing the charging in MP (medium pressure) separator 359 can be less than 70 DEG C, such as 50 DEG C or lower. Pressure in MP (medium pressure) separator 359 can be 1200 to 2500psig (8,375 to 17,339kPa), such as 1500 to 1800psig (10,433 to 12,512kPa).

In pipeline 360 from the overhead vapor stream of MP (medium pressure) separator 359 except hydrogen, also comprise ammonia. As shown in Figure 6, by reclaiming ammonia with the steam in adiponitrile washing pipeline 360 in adiponitrile resorber 361. In figure 6 in another embodiment unshowned, it is possible to the overhead vapor stream at least partially from MP (medium pressure) separator 359 is directed to high pressure absorber 399, in described high pressure absorber, reclaim ammonia by washing steam flow with water.

The pressure of the liquid efflunent from MP (medium pressure) separator 359 is made to be reduced to ammonia further by the pressure of flash distillation subsequently in charging separator 364. As shown in Figure 6, via pipeline 365 with the streamed removal vaporous ammonia of top material from charging separator 364. Temperature in charging separator 364 can be 50 DEG C or lower, such as 15 DEG C to 50 DEG C. Pressure in charging separator 364 can be 450 to 600psig (3,204 to 4,238kPa), such as 500 to 600psig (3,549 to 4,238kPa), such as 550psig (3,893kPa).

In order to promote to remove ammonia further from from the liquid bottom streams of charging separator 364, by the streams heating at least 50 DEG C in pipeline 332, such as at least 100 DEG C. As shown in Figures 5 and 6, this is heated by and makes the streams in pipeline 332 pass to heat regenerator 329,339 and 350 generation. When a part of ammonia vaporization in heat regenerator during heating liquid, in liquid. This arrives steam water cooler 375 through the ammonia of vaporization through pipeline 331. Liquid stream through heating passes pipeline 333 to withdrawer tailings tank 367 from heat regenerator. The temperature of the streams in pipeline 333 can be 75 DEG C to 180 DEG C, such as 120 DEG C. Similarly, the temperature of the liquid in withdrawer tailings tank 367 and flasher 373 can be 130 DEG C to 180 DEG C, such as 170 DEG C. According to optional embodiment unshowned in Fig. 5 and 6, except one or more heat regenerator or replace one or more heat regenerator, it is also possible to use steam as thermal source. For example, steam water cooler 375 and flasher 373 can be replaced with distillation tower, and in the heating member that streams can be introduced distillation tower or reboiler.

Temperature in steam water cooler can be 40 DEG C to 80 DEG C, such as 50 DEG C to 60 DEG C. Temperature in primary flash tank 380 can be 110 DEG C to 170 DEG C, such as 140 DEG C to 150 DEG C. Temperature in two-stage flash tank 382 can be lower than the temperature in primary flash tank 380 10 DEG C to 50 DEG C. Temperature in two-stage flash tank 382 can be 100 DEG C to 150 DEG C, such as 140 DEG C. The temperature finely tuned in separator 394 and ammonia receptor 396 can be 15 DEG C to 45 DEG C, such as 35 DEG C.

Pressure in withdrawer tailings tank 367, flasher 373 and steam water cooler 375 can than the pressure little 5 in withdrawer charging separator 364 to 70psig (136 to 584kPa). Pressure in withdrawer tailings tank 367, flasher 373 and steam water cooler 375 can be 400 to 550psig (2,859 to 3,893kPa), such as 475 to 500psig (3,204 to 3,549kPa). Pressure in primary flash tank 380 can be 25 to 50psig (274 to 446kPa), such as 30 to 42psig (308 to 391kPa). Pressure in two-stage flash tank 382 can be 0 to 25psig (101 to 274kPa), such as 0 to 10psig (101 to 170kPa).

Pressure in ammonia receptor 396 can be 300 to 600psig (2,170 to 4,238kPa), such as 400 to 500psig (2,859 to 3,549kPa).

High pressure absorber 399 is designed to handle high voltages steam flow and low-pressure absorber 413 is designed to process low-pressure steam stream. Pressure in high pressure absorber 399 can be 120 to 180psig (929 to 1,342kPa), such as 150psig (1,136kPa). Pressure in low-pressure absorber 413 can be 0 to 50psig (101 to 446kPa), such as 0 to 10psig (101 to 170kPa).

It is converted into the most of ammonia being used as thinner in hexamethylene-diamine (HMD) to reclaim from the headpiece stream of steam water cooler 375 along pipeline 390 with anhydrous ammonia form at adiponitrile (ADN). But, by washing with water, ammonia-containing gas reclaims some ammonia. The gas washed can comprise such as hydrogen and methane further. The object of washing is dual, namely reduces atmospheric pollution and reclaims ammonia.

Two systems are used to reclaim ammonia from air-flow. A system uses high pressure absorber (HPA) and another system use low-pressure absorber (LPA). In the figure 7, these resorbers are represented by HPA399 and LPA413.

The high pressure absorber below bottom tray or packaging section can be entered containing ammonia flow. Can add and adjust purified water and/or recycled water controls the ammonia (NH in leaving the temperature of gas of high pressure absorber 399 via pipeline 401 and leaving the ammonia aqua stream of high pressure absorber 399 via pipeline 405₃) concentration. Current in pipeline 400 can enter the high pressure absorber 399 at washer top above distribution plate. This water flows down through filler and absorbing ammonia (NH₃). When water absorbing ammonia, give out heat. Such as hydrogen (H₂) and methane (CH₄) uncondensable gas leave at the top of washer. Any liquid carried secretly can be trapped within exhaust-steam separator or Purge gas separator 402, and containing H₂Or CH₄Gas may be directed to the combustion tower can being positioned at outside field, incinerator or boiler.

The ammoniacal liquor tailings of high pressure absorber 399 can circulate by air or watercooler (not illustrating in Fig. 7) and be sent to ammoniacal liquor hold-up vessel 409. The content liquid of valve to control in high pressure absorber 399 can be used.A part can return high pressure absorber 399 via pipeline 407 and 408 through the ammonia aqua stream of cooling. The ammonia aqua stream returning high pressure absorber 399 via pipeline 408 can return high pressure absorber 399 to remove absorption heat.

Ammonia (the NH in the ammonia soln of high pressure absorber 399 is left via pipeline 405₃) concentration can control at predeterminated level. For example, the concentration of the ammonia in this solution can be 20wt% to 22wt%. Depend on the configuration of equipment used in technique, the excessive use of steam in ammonia distillation tower 424 can be caused lower than the ammonia density of 20wt%. In addition, ammonia density higher than 23wt% can cause the excess exhaust gases in ammoniacal liquor hold-up vessel 409.

Low-pressure absorber 413 (LPA) can from the one or more middle reception steam primary flash tank 380 and two-stage flash tank 382. When ammonia strainer (for removing particulate from ammonia recirculation flow) with when ammonia pump is out of service, they can also reduce pressure LPA413.

Low-pressure absorber 413 is washed off the ammonia in the steam introduced in low-pressure absorber 413. A large amount of ammonia circulation stream can be maintained by means of recycle pump 420, described recycle pump is from the bottom pumping liquid of low-pressure absorber 413 through air or watercooler (not illustrating Fig. 7), and returns to the top of low-pressure absorber 413 subsequently via divider. Downward liquid flow is through filler and absorbs upwards through the ammonia (NH of filler₃) steam.

Can control low-pressure absorber 413 bottom fluid level with allow a part ammonia soln flow to ammoniacal liquor hold-up vessel 409.

Ammonia (the NH in the ammonia soln of low-pressure absorber 413 is left via pipeline 419₃) concentration can control with identical predetermined concentration level in high pressure absorber 399. For example, the concentration of the ammonia in this solution can be 20wt% to 22wt%.

Steam can flow over the ventilation washer at the top being positioned at low-pressure absorber 413. From process water hold-up vessel 414 recycled water can the top of feed-in ventilation washer, and the bottom of filler to tower can be flowed down through. Liquid from the bottom of low-pressure absorber 413 can be pumped into low-pressure absorber water cooler (not illustrating in Fig. 7) by tailings pump 420.

The gas not absorbed leaves the top of ventilation washer, it is possible to be directed to combustion tower, boiler or other combustion unit via pipeline 418.

The detailed description of Fig. 8 A

Fig. 8 A shows the example of the mode reclaiming purified diamines product from rough diamines product. It is understood that the feature presented in Fig. 8 A is schematic and is not draw in proportion. Recovery process shown in Fig. 8 A is particularly useful for reclaiming hexamethylene-diamine.

In fig. 8 a, via pipeline 450, rough diamines product is passed in low-boiling-point substance distillation section 451. Diamines incoming flow in pipeline 450 can corresponding to the outflow logistics in the pipeline 385 of Fig. 6. Distilling in section 451 at low-boiling-point substance, the compound in pipeline 450 is separated into two streams, represents by pipeline 452 and 454 in fig. 8 a. Compound in pipeline 452 comprises the compound of boiling point lower than the boiling point of the diamines in pipeline 450. Compound in pipeline 454 comprises boiling point lower than the compound with the boiling point higher than the diamines in pipeline 450. Pipeline 454 mid-boiling point can in the 50 of the boiling point of diamines DEG C lower than the boiling point at least partially of these compounds of diamines.

Streams in pipeline 450 is included in the compound for " low-boiling-point substance ", " in boil thing ", diamines and " high boiling material " following by definition.Streams in pipeline 450 can comprise at least 95wt%, such as the diamines of at least generation in dinitrile hydrogenation of 97wt%. The example of low-boiling-point substance comprises ammonia and water. The example of high boiling material comprises the oligopolymer of diamines and amino-nitrile, as when in two itrile groups on dintrile only one be hydrogenated time produce hydrogenated products.

When diamines is hexamethylene-diamine (HMD), high boiling material comprises two (hexa-methylene) triamine. When diamines is hexamethylene-diamine (HMD), in the thing that boils comprise one or more isomer of diamino-cyclohexane (DCH). The example of the isomer of diamino-cyclohexane (DCH) is 1,2-diamino-cyclohexane.

When diamines is 2-methyl pentamethylene diamine (MPMD), high boiling material comprises two (2-methyl five methylene radical) triamine. When diamines is 2-methyl pentamethylene diamine (MPMD), in the thing that boils comprise the one in the multiple isomer of methyl ring pentamethylene diamine (MCPD).

Outflow logistics in the pipeline 385 of Fig. 6 is corresponding to the charging in the pipeline 450 of Fig. 8 A. Outflow logistics in pipeline 385 can by one or more heating phase before introduce low-boiling-point substance distillation section 451 via pipeline 450. For example, the streams in pipeline 385 can pass through the first heat exchanger, and in described first heat exchanger, it carries out thermo-contact with the outflow logistics 454 from low-boiling-point substance distillation section 451. The streams of this heat exchanger in order to heat in the streams and cooling pipeline 454 of pipeline 385. The effluent through heating from the first heat exchanger can pass through two heat exchangers subsequently. Steam can be used in two heat exchangers to heat the charging leading to low-boiling-point substance distillation section 451 further.

Low-boiling-point substance distillation section 451 can operate under air or vacuum condition. The temperature curve in first in one or more towers in low-boiling-point substance distillation section 451 can so that the compound of the boiling point or more lower boiling (namely 100 DEG C or lower) with water be once enter described tower tend and flash off. When this kind of tower operates in atmospheric conditions, it is possible to promote this kind of flash distillation by the outflow logistics in pipeline 385 being heated to 110 DEG C of temperature to 150 DEG C, such as 130 DEG C. Any tower in low-boiling-point substance distillation section 451 can be connected to provide heat at least partially to distill with heat exchanger, heating member or reboiler (not illustrating in Fig. 8 A) fluid.

Low-boiling-point substance distillation section 451 in distillation condition can so that at least 95% via one or more streams represented by pipeline 450 enter low-boiling-point substance distillation section 451 diamines exit in streams 454. Distillation condition can also make at least 99wt%, such as at least the boiling point of 99.5wt% is that the compound of 100 DEG C or lower exits in one or more overhead vapor stream along pipeline 452. Low-boiling-point substance distillation section 451 can operate when certain class, and described condition makes maximum 5%, and the diamines entered in low-boiling-point substance distillation section 451 of such as 0.1% to 1% passes to one or more headpiece stream, represents for pipeline 452 in fig. 8 a. In this way it would be possible, the loss of the diamines in pipeline 452 drops to minimum.

One or more streams comprising one or more high boiling material is distilled section 451 from low-boiling-point substance and is obtained, through one or more pipeline represented by pipeline 454 in boil thing distillation section 460. Streams in pipeline 454 can also contain diamines, in boil thing and low-boiling-point substance, be entrained with high boiling material. Streams in pipeline 484 contains diamines and high boiling material, and it distills in section 455 at high boiling material and is separated.The streams comprising the compound with high boiling material distills section 455 through pipeline 456 from high boiling material. The streams comprising diamines distills section 455 through pipeline 458 from high boiling material.

Comprise diamines and in the boil streams of thing distill section 451 from low-boiling-point substance and obtain, through pipeline 454 in boil thing distillation tower 460.

In the thing distillation tower 460 that boils can operate under vacuum. In the outlet pressure in thing distillation tower 460 of boiling can be 40 to 120mmHg (6.7 to 16kPa), such as 50 to 70mmHg (10.7 to 13.3kPa).

Liquid phase exits via therefrom the boil bottom section of thing distillation tower 460 of pipeline 484. A part of streams in pipeline 484 can by pump and enter heating member (not illustrating in Fig. 8 A). Steam can be used as the thermal source of heating member. Heating member can have pump circulation loop design or thermal siphon design. Pump can provide stable flow of material and enough back pressures (such as 20 to 30psig, namely 239 arrive 308kPa) in order to avoid material seethes with excitement. Can boil in returning thing distillation tower 460 through heating liquid from heating member. Liquid stream from heating member can boil in thing distillation tower 460 in passing to via restricted orifice. Vaporization is upwards entered in tower by the compound that boiling point is minimum, and more the compound of high boiling point is by the bottom of the thing distillation tower 460 that boils in returning.

In boil thing distillation tower 460 top near two column plates are installed. Lower tray is liquid header column plate 461. This column plate 461 is collected liquid from top and is contacted with the steam upwards advanced tower. The liquid collected from top in liquid collecting column plate 461 comprises the backflow returning stream and introducing via 487 introduced via pipeline 467 from heat exchanger 466. Roughly temperature on liquid collecting column plate 461 can be 115 DEG C to 125 DEG C, such as 121 DEG C. Liquid is pumped into pipeline 465 via pump 464 from pipeline 463 and enters heat exchanger 466.

Heat exchanger 466 can be positioned at in boil thing distillation tower 460 very close to or position relatively far away. For example, heat exchanger 466 and in the thing distillation tower 460 that boils can be arranged in identical or different buildings or shell.

Boiling before thing distillation tower 460 in liquid returns via pipeline 467, the reducing amount of the temperature entering the liquid in the streams of heat exchanger 466 in heat exchanger 466 can be 15 DEG C to 35 DEG C, such as 20 DEG C to 30 DEG C. Returning stream and can return during a certain position above column plate 462 enters, at top liquid, the thing distillation tower 460 that boils via pipeline 467. Backflow can also return during a certain position above column plate 462 enters, at top liquid, the thing distillation tower 460 that boils. This backflow can be boiled in entering via pipeline 487 thing distillation tower 460.

From in the boil overhead vapor of thing distillation tower 460 return column plate 462 and enter condenser subsequently, such as air pressure type spray condenser 475, the condensation in described condenser of described steam through top liquid. These steams thing distillation tower 460 that therefrom boils is represented by pipeline 474 in fig. 8 a to the conveying of air pressure type spray condenser 475. Pipeline 474 in Fig. 8 A enters rectangle at rectangular base, and described rectangle describes air pressure type spray condenser 475. But, this kind is described to be only that a kind of figure represents. From in the boil steam of thing distillation tower 460 can enter air pressure type spray condenser 475 via each position. For example, these steams can near the top of condenser 475 or near-bottom enter air pressure type spray condenser 475.Air pressure type spray condenser 475 can by also stream as mentioned below or reflux type operation. Air pressure type spray condenser 475 can operate under air or vacuum condition.

Steam through condensation leaves from air pressure type spray condenser 475, through pipeline 476, to pipeline 478 and enters heat exchanger 480 through pump 477 subsequently. The liquid entering heat exchanger 480 via pipeline 478 can cool at least 5 DEG C before leaving heat exchanger 480 via pipeline 481, such as 5 DEG C to 20 DEG C. The temperature entering the liquid of heat exchanger 480 via pipeline 478 can be 75 DEG C to 90 DEG C, such as 80 DEG C to 90 DEG C. The temperature leaving the liquid of heat exchanger 480 via pipeline 481 can be 65 DEG C to 85 DEG C, such as 70 DEG C to 80 DEG C.

Via pipeline 482, cooling fluid is introduced in heat exchanger 480. Cooling fluid can be air or water. , it is possible to via pipeline 482 at 35 DEG C to 50 DEG C, for example such as, at the temperature of 40 DEG C to 45 DEG C, heat exchanger 480 introduces liquid water. Entering the water coolant in heat exchanger 480 via pipeline 482 can make temperature increase by 2 DEG C to 20 DEG C, such as 2 DEG C to 10 DEG C before leaving via pipeline 483 in heat exchanger 480.

Process flow in pipeline 481 is poured in air pressure type spray condenser 475 by spray. Pipeline 481 in Fig. 8 A enters rectangle in rectangular top, and described rectangle describes air pressure type spray condenser 475. But, this kind is described to be only that a kind of figure represents. Liquid spray can enter air pressure type spray condenser 475 via each position. For example, these steams can near the top of condenser 475 or near-bottom enter air pressure type spray condenser 475. Air pressure type spray condenser 475 can by also flowing or reflux type operation. When air pressure type spray condenser 475 is by, when also stream mode operates, spraying can be introduced in condenser 475 in the position entering position less than or equal to the steam introduced via pipeline 474. When air pressure type spray condenser 475 presses reflux type operation, spraying can be introduced in condenser 475 in the position entering position higher than the steam introduced via pipeline 474. And the example of gas pressure type spray condenser is described in No. 5,516,922nd, United States Patent (USP). The example of adverse current air pressure type spray condenser is described in No. 2,214,932nd, United States Patent (USP).

As shown in Figure 8 A, comprise the distillate flow such as the thing that boils in diamino-cyclohexane (DCH) to remove from pipeline 478 in streams 479.

Distillate flow can be taken out (before or after air/water water cooler) from liquid and is used as tower backflow. For example, this distillate flow can obtain from pipeline 476, pipeline 478, pipeline 479 or pipeline 481. Withdrawing fluid in this distillate flow can boil in thing distillation tower 460 in the position returning column plate 462 higher than top liquid is introduced. Streams for the thing distillation tower 460 that boils in making backflow return is depicted as in fig. 8 a through pipeline 487.

The boiling point of hexamethylene-diamine is 205 DEG C. When making adiponitrile hydrogenation to manufacture hexamethylene-diamine, about by product, define the various isomer of diamino-cyclohexane, such as 1,2-diamino-cyclohexane. The boiling point of these isomer of diamino-cyclohexane can be such as in the scope of 185 DEG C to 195 DEG C. These isomer of diamino-cyclohexane boil in being thing. Make adiponitrile hydrogenation in the technique manufacturing hexamethylene-diamine, these isomer of diamino-cyclohexane mainly in boil thing distillation tower 460 be separated with hexamethylene-diamine.

The boiling point of methyl pentamethylene diamine is 194 DEG C. When making methyl cellosolve acetate glutaronitrile hydrogenation to manufacture methyl pentamethylene diamine, about by product, define the various isomer of methyl ring pentamethylene diamine. The boiling point of these isomer of methyl ring pentamethylene diamine can be such as in the scope of 180 DEG C to 187 DEG C. These isomer of methyl ring pentamethylene diamine boil in being thing. Make methyl cellosolve acetate glutaronitrile hydrogenation with in the technique manufacturing methyl pentamethylene diamine, these isomer of methyl ring pentamethylene diamine mainly in boil thing distillation tower 460 be separated with methyl pentamethylene diamine.

The streams comprising refining diamines product obtains from high boiling material distillation tower 455 with distillate flow form via pipeline 458. Although not illustrating in Fig. 8 A, but a part of streams in pipeline 484 can be pumped in heat exchanger, heating member or reboiler and heat. The streams through heating coming automatic heat-exchanger, heating member or reboiler can be boiled thing distillation tower 460 in the position drawing position higher than pipeline 484 returns. In the thing that boils concentrated in purification thickener tower 485, and leave system with headpiece stream 486 form. The bottoms stream of tower 485 returns tower 460 as reflux via pipeline 488.

Heat exchanger 466 in Fig. 8 A is corresponding to the heat exchanger 318 in Fig. 4. The charging introducing heat exchanger 466 in Fig. 8 A via pipeline 468 introduces the charging in heat exchanger 318 corresponding in Fig. 4 via pipeline 308. The charging introducing heat exchanger 466 in Fig. 8 A via pipeline 465 introduces the charging in heat exchanger 318 corresponding in Fig. 4 via pipeline 319.

In Fig. 8 A via pipeline 469 leave heat exchanger 466 through add hot feed corresponding in Fig. 4 via pipeline 321 leave heat exchanger 318 through adding hot feed. In Fig. 8 A via pipeline 467 leave heat exchanger 466 through cooling charging corresponding in Fig. 4 via pipeline 320 leave heat exchanger 318 through cooling charging.

The temperature of the charging in pipeline 468 can increase by 27 DEG C to 47 DEG C, such as 32 DEG C to 42 DEG C in heat exchanger 466, thus the charging leaving heat exchanger 466 via pipeline 469 is heated.

Heat exchanger 470 in Fig. 8 A is corresponding to the heat exchanger 323 in Fig. 4. The charging introducing heat exchanger 470 in Fig. 8 A via pipeline 469 introduces the charging in heat exchanger 323 corresponding in Fig. 4 via pipeline 321. The temperature of the charging in pipeline 469 can increase by 2 DEG C to 10 DEG C, such as 1 DEG C to 5 DEG C in heat exchanger 470, thus the charging leaving heat exchanger 470 via pipeline 473 is heated. Charging through heating can be introduced in convertor 327 via pipeline 326 subsequently, as shown in Figures 4 and 5.

In order to the charging in pipeline 468 is heated to produce the charging through heating in pipeline 473 and the amount of the heat energy that applied by heat exchanger 466 (such as by kilowatt-hour in units of) can be 80% to the 99% of the total heat energy applied to charging by heat exchanger 468 and heat exchanger 470, such as 90% to 99%, such as 92% to 98%.

The detailed description of Fig. 8 B

An embodiment of the low-boiling-point substance distillation section 451 of Fig. 8 B show Fig. 8 A. Specific distillation section in Fig. 8 B comprises two distillation towers 490 and 492. However, it should be appreciated that the low-boiling-point substance distillation section 451 of Fig. 8 A can comprise different distillation tower configurations, comprise single distillation tower or two or more distillation tower.

As seen in fig. 8b, rough diamines stream enters the first distillation tower 490 through pipeline 450.Via pipeline 452 from the first distillation tower 490 with the streamed removal of top material from the low-boiling-point substance at least partially in the streams of pipeline 450.

Comprise diamines, in the boil bottoms stream of thing and high boiling material obtain from the first distillation tower 490 and pass to second column 492 via pipeline 491. In second column 492, diamines with in the thing that boils be separated with high boiling material. Diamines and in the thing that boils obtain from second column 492 with overhead vapor form via pipeline 454. As shown in Figure 8 A, boil in the streams feed-in in pipeline 454 in thing distillation tower 460.

Obtain side via pipeline 453A from second column 492 and get streams. Bottoms stream is obtained from second column 492 via pipeline 453B. These streams are all introduced in high boiling material distillation section 455 (shown in Fig. 8 A). As seen in fig. 8b, via pipeline 496, from high boiling material, recirculation flow is distilled section to introduce second column 492. Streams in pipeline 496 can get lower than side streams 453A draw position and the position drawing position higher than bottoms stream 453B is introduced in second column 492.

Although Fig. 8 B does not illustrate, it is to be appreciated that, a part of overhead vapor stream in pipeline 452 can pass to condenser and phlegma can return the first distillation tower 490 by backflow form at least partially. Fig. 8 B does not illustrate the heating member for providing heat for distilling or reboiler yet. For example, a part of streams in pipeline 491 can be introduced in the first distillation tower in the position of the introducing position lower than the incoming flow in pipeline 450 by heating member or reboiler and through the fluid of heating.

The detailed description of Fig. 8 C

Fig. 8 C shows an embodiment of the high boiling material distillation section 455 of Fig. 8 A. Specific distillation section in Fig. 8 C comprises two distillation towers 493 and 495. However, it should be appreciated that the high boiling material distillation section 455 of Fig. 8 A can comprise different distillation tower configurations, comprise single distillation tower or two or more distillation tower.

In Fig. 8 C, via pipeline 453A, the first incoming flow comprising the thing that boils at least one, diamines and at least one high boiling material is introduced in the first distillation tower 493. As seen in fig. 8b, the streams in pipeline 453A is got streams form with side and is obtained from distillation tower 492. The 2nd incoming flow comprising diamines and at least one high boiling material is introduced in second column 495 via pipeline 453B. As seen in fig. 8b, the streams in pipeline 453B obtains from distillation tower 492 with bottoms stream form.

The vaporous top material comprising the thing that boils at least one flows through and obtains from first distillation tower 493 of Fig. 8 C by pipeline 457. The liquid side comprising diamines is got streams and can be obtained from the first distillation tower 493 via pipeline 458A.

Liquid bottom streams obtains from first distillation tower 493 of Fig. 8 C via pipeline 496 and returns the second column 492 of Fig. 8 B. As seen in fig. 8b, the streams in pipeline 496 higher than the bottoms stream in pipeline 453B draw position and lower than in pipeline 453A side stream draw position position introduce.

Streams in pipeline 453B can higher than the bottoms stream in pipeline 456 draw position and the position drawing position lower than the overhead vapor stream in pipeline 458B is introduced in second column 495. Bottoms stream in the pipeline 456 of Fig. 8 C is corresponding to the streams in the pipeline 456 of Fig. 8 A. Streams in pipeline 456 comprises at least one high boiling material. The high boiling material in streams in pipeline 456 can refine the various components to be separated in described streams further in Fig. 8 A with 8C in unshowned step.

Overhead vapor stream in pipeline 485B can pass to unshowned diamines hold-up vessel in Fig. 8 C. Similarly, the streams pipeline 485A in Fig. 8 C can pass to unshowned diamines hold-up vessel in Fig. 8 C. In addition, the streams in the pipeline 484 of Fig. 8 A can pass to unshowned diamines hold-up vessel in Fig. 8 A. Can be identical or different for storing the hold-up vessel of the inclusion of these three streams. For example, these three streams can pass to a common hold-up vessel.

A part for any streams in pipeline 458A, 458B and 484 can return in any one in tower 460 (shown in Fig. 8 A), tower 493 (shown in Fig. 8 B) and tower 495 (shown in Fig. 8 C). For example, these three streams all can be stored in a common hold-up vessel, and a part for this diamines jointly stored can return the distillation tower 495 in Fig. 8 C together with backflow.

Overhead vapor stream in pipeline 457 and 458B can pass through condenser (not illustrating in Fig. 8 C) and part phlegma can return distillation tower 493 and 458B by backflow form. In addition, a part of bottoms stream in pipeline 496 and 456 can pass through heat exchanger, reboiler or heating member (not illustrating in Fig. 8 C) and a part can return distillation tower 493 and 458B in the position of the introducing position lower than incoming flow 453A and 453B through heating fluid.

The detailed description of Fig. 9

Fig. 9 shows the revision of the technique shown in Fig. 8 A. Specifically, the feature from Fig. 8 A is eliminated in fig .9. These elliptical features comprise column plate 461, column plate 462, pipeline 463, pump 464, pipeline 465, heat exchanger 466 and pipeline 467. In fig .9, the fluid in pipeline 468 directly enters heat exchanger 470, instead of first preheating in heat exchanger 466.

Moveable catalyzer cylinder and convertor container

As previously mentioned, hydrogenation catalyst can be contained in moveable catalyzer cylinder. Hereinafter with reference Figure 10 describes the example of this kind of catalyzer cylinder and its purposes in convertor container to 16.

The detailed description of Figure 10

Figure 10 is the plan view of the catalyzer cylinder with cylinder-shaped sleeve 600, it has top 602, bottom 604, bottom comprises and enters the ingate 610 of central vertical pipe 611 (do not illustrate in Figure 10, but show in figs. 12 and 13) and one or more outlet opening 608 for chemical product for chemical reactant. Chemical reaction all occurs in barrel 600, it is possible to easily get rid of ambient air from described barrel.

The detailed description of Figure 11 and Figure 12

Figure 11 is the side-view of the structure of Figure 10, and Figure 12 is the sectional view of Figure 11 along line 3-3, presents the internal structure of catalyzer cylinder. The inlet tube 613 of coupling is inserted in vertical tube 611 via ingate 610. Chemical reactant upwards flows over the top that vertical tube 611 arrives reactor barrel 600. The upper end top cover of reactor barrel 600 covers, and described top cover is tightened with bolt on barrel top. Top cover and bolt are not for clarity sake shown.

The upper end of vertical tube 611 almost extend to barrel top and higher than the top of catalyst bed (for clarity sake not illustrating), the chemical reactant entering barrel is made to be transported to the top of catalyst bed, it can pass catalyst bed by gravity leakage, and the promotion by the pressure of reaction-ure feeding. In order to the reaction-ure feeding evenly distribute that will enter is at the top of catalyst bed, the upper end of vertical tube 611 can be equipped with back taper sieve 612 so that chemical reactant leaves the top of vertical tube 611 and sieves 612 distribution via back taper.Or, close the upper end of vertical tube 611 and bore out a round 614 to provide fluid outlet at riser upper end circumference so that chemical reactant is by the top of evenly distribute at catalyst bed. In a rear embodiment, this round 614 should surround with screen cloth (for clarity sake not illustrating) so that reactant can leave vertical tube, but catalyst pellet's or particle can not enter and can not block vertical tube. Hole 614 extends beyond the level of catalyst bed at least partially. Hole 614 can also be positioned at the lower section of the top layer of catalyst bed at least partially.

After catalyst bed, there is reaction and be converted to chemical product in chemical reactant, described chemical product by first along outlet distributor pipeline 618 by perforation or screen cloth, subsequently under enter the collection channel (not illustrating in Figure 11 and 12) of bottom of the bottom 604 being connected to barrel 600 and leave barrel. Outlet distributor pipeline 618 can comprise the hole surrounded by screen cloth. Product leaves via one or more delivery pipe (not illustrating in Figure 11 and 12) subsequently and enters bottom barrel and void space between convertor inside bottom (as shown in Figure 15 B). Collect subsequently and process chemical product further.

The detailed description of Figure 13 A

Figure 13 A is the plan view of convertor 630 container (being hereafter called " convertor ") using catalyzer cylinder in hydrogenation. Convertor is shown from bottom.

During the hydrogenation carried out at high temperature and pressure, convertor makes cartridge wall strengthen. Cartridge wall is designed to provide enough light weight, because wall must can only bear the pressure reduction at catalyst bed two ends. If cartridge wall is designed to when bearing temperature and the pressure condition of hydrogenation without when strengthening, so practical situation are that barrel will be too heavy so that cannot insert, transport and move out.

Convertor 630 entirety is substantially cylindrical, has base section 632, centre portions 638 and top section 640. The diameter of this top section 640 can slightly larger than the rest part of described device. Inlet tube 634 and at least one outlet opening 636 of location placed in the middle penetrate base section 632.

The detailed description of Figure 13 B

Figure 13 B is the decomposition view of the convertor of Figure 13 A, and it is shown in addition, and inlet tube 634 is made up of at least three different parts: for being connected to the inlet tube joint flange 634a entering pipeline of chemical reactant fluid; It is configured for the inlet tube insertion portion 634b that the diameter of the inside of the central vertical pipe 652 of adaptive catalyzer cylinder reduces; And the joint flange 634c so as to bolt, inlet tube is tethered to convertor 630 bottom. The top section 640 of convertor has set collar 644, has breech lock thread 646 on its excircle.

The detailed description of Figure 14 A and Figure 14 B

Figure 14 A is the side-view of convertor 630, and Figure 14 B is the sectional view of Figure 14 A, and it show in more detail whole converter system. For example, in Figure 14 b, it is visible that the fluid between outlet opening 636 and the internal voids 632a of low portion 632 is connected, as the overall arrangement of inlet tube 634. Similarly, the internal arrangement of top section 640 can also be seen in cross sectional view. Convertor top cover 620 is positioned at above catalyzer cylinder 600. Being placed in convertor by the vertical tube 652 settled between two parties so that the lower end of vertical tube 652 coordinates the upper end 634b of inlet tube 634, described combination provides the fluid sealed entry (for clarity sake not illustrating) of chemical reactant to catalyzer.Described in following, by the set collar 644 of bolt lock mechanism 648, convertor top cover 620 is fixed in position.

At catalyzer cylinder bottom stream to the outlet opening 650 of collection channel (not illustrating in Figure 14 B) for chemical product provides outlet.

Convertor top section 640 containing bolt lock mechanism 648, the breech lock tooth 642 that its inner periphery being included in top section 640 is formed with formed on its excircle there is cooperating breech lock tooth 646 consolidate the combination holding ring 644. When along first party to engagement and when rotating, convertor top cover 620 is locked in position by bolt lock mechanism 648. When rotated in the opposite direction, bolt lock mechanism 648 discharges convertor top cover 620 and set collar 644, and convertor top cover 620 can be mentioned from convertor 630, it is provided that lead to the entrance of the catalyzer cylinder 600 used up.

The detailed description of Figure 15

Figure 15 is the plan view of the lockout mechanism of convertor, and it is made up of shell 660 and internal plug, in this case, described internal plug be configured for be inserted in shell and part rotate to enter line-locked set collar 662. Shell 660 has cylindrical form interior surface and the first end surface 666 at one end. Cylindrical form interior surface contains the first breech lock screw thread 672 being made up of 2 to 20 equidistant lock rings, and each lock ring comprises m row tooth 672a and m gap 672b, and described tooth and described gap are around cylindrical form interior surface alternately configuration.

Set collar 662 has the 2nd breech lock screw thread 668, and it comprises gap 668b and the m row tooth 668a that quantity is m, and its quantity is equal with the quantity of conduit, and around the alternately configuration of its cylindrical outer surface 670, wherein m is 2 to 12. Inserting at set collar 662 after in the space of shell 660, on set collar 662, this several row tooth 668a is directed at the gap 672b on the internal surface of shell 660, and set collar 662 is moved axially in shell 660. In order to lock the bolt lock mechanism of so formation, set collar 662 part is rotated so that its breech lock screw thread/tooth 668a passes in the breech lock screw thread/tooth 672a of conduit and between described breech lock screw thread/tooth, thus cooperation is to be in axial direction fixed to set collar 662 in shell 660.

The detailed description of Figure 16

In figure 16, being incorporated to by bolt lock mechanism on chemical reactor encloses container 660, the positioned inside of described chemical reactor encloses container has catalyzer cylinder 600, and described chemical reactor encloses container is connected fluid communication with the entrance and exit on the bottom of described barrel. Convertor top cover 620 is placed in below the bottom of set collar 662 so that the rotation of bolt lock mechanism and locking are for being fixed on set collar 662 in shell 660. The clean liquid flow of inflow and outflow barrel is represented by the arrow in Figure 16.

Example

Following instance describes and makes dinitrile hydrogenation produce the method for diamines and the method for the catalyzer for the preparation of this hydrogenation.

Example 1

This example describes the conversion of methyl cellosolve acetate glutaronitrile (MGN) to 2-methyl pentamethylene diamine (MPMD). With reference to figure 1, the incoming flow comprising MGN and fresh feed and recycled hydrogen and ammonia are passed in a series of four convertors 42,44,46 and 48. MGN charging can have following composition:

MGN=99.1wt%min

ESN=0.4wt%max

HCN=20ppmmax

Water=0.12wt%max

Ethylene glycol=50ppmmax

Phosphorus=15ppm

Other=0.7wt%max

The pressure leading to the charging of the first convertor 42 can be at least 3500psig (24,233kPa), such as at least 4000psig (27,680kPa), such as at least 4500psig (31,128kPa).The temperature of the charging leading to the first convertor can be at least 100 DEG C, such as at least 105 DEG C, such as at least 110 DEG C. In the first convertor 42, the reaction of hydrogen and MGN is thermopositive reaction. Therefore, the temperature of the outflow logistics leaving the first convertor 42 can be higher at least 5 DEG C than the temperature of the streams entering the first convertor 42, such as at least 10 DEG C. The temperature of the streams leaving the first convertor 42 preferably should be no more than 200 DEG C, such as 190 DEG C, such as 180 DEG C.

Before the outflow logistics from the first convertor 42 is introduced in the 2nd convertor 44, it is preferable that make it cool at least 5 DEG C, such as at least 10 DEG C. This kind of cooling can at least in part by making the effluent from convertor 42 pass at least one heat exchanger or water cooler (not shown in figure 1) and by being undertaken in fresh MGN charging (its temperature is lower than the temperature of the effluent from convertor 42) introduction pipe line 50 via pipeline 38.

The pressure leading to the charging of the 2nd convertor 44 can be at least 3500psig (24,233kPa), such as at least 4000psig (27,680kPa), such as at least 4500psig (31,128kPa). The temperature of the charging leading to the 2nd convertor 44 can be at least 100 DEG C, such as at least 105 DEG C, such as at least 110 DEG C. In the 2nd convertor 44, the reaction of hydrogen and MGN is thermopositive reaction. Therefore, the temperature of the outflow logistics leaving the 2nd convertor can be higher at least 5 DEG C than the temperature of the streams entering the 2nd convertor 44, such as at least 10 DEG C. The temperature of the streams leaving the 2nd convertor 44 preferably should be no more than 200 DEG C, such as 190 DEG C, such as 180 DEG C.

Before the outflow logistics from the 2nd convertor 44 is introduced in the 3rd convertor 46, it is preferable that make it cool at least 5 DEG C, such as at least 10 DEG C. This kind of cooling can at least in part by making the effluent from the 3rd convertor 46 pass at least one heat exchanger or water cooler (not shown in figure 1) and by being undertaken in fresh MGN charging (its temperature is lower than the temperature of the effluent from the 2nd convertor 44) introduction pipe line 52 via pipeline 40.

The pressure leading to the charging of the 3rd convertor 46 can be at least 3500psig (24,233kPa), such as at least 4000psig (27,680kPa), such as at least 4500psig (31,128kPa). The temperature of the charging leading to the 3rd convertor can be at least 100 DEG C, such as at least 105 DEG C, such as at least 110 DEG C. In the 3rd convertor 46, the reaction of hydrogen and MGN is thermopositive reaction. Therefore, the temperature of the outflow logistics leaving the 3rd convertor 46 can be higher at least 5 DEG C than the temperature of the streams entering the 3rd convertor 46, such as at least 10 DEG C. The temperature of the streams leaving the 3rd convertor 46 preferably should be no more than 200 DEG C, such as 190 DEG C, such as 180 DEG C.

Before the outflow logistics from the 3rd convertor 46 is introduced in the 4th convertor 48, it is preferable that make it cool at least 5 DEG C, such as at least 10 DEG C. This kind of cooling can at least in part by making to enter in pipeline 56 from the effluent of the 3rd convertor 46 through pipeline 54 and heat exchanger 20 to carry out. The temperature of the streams in pipeline 56 can by reducing in fresh MGN charging (its temperature is lower than the temperature of the effluent from the 3rd convertor 46) introduction pipe line 56 via pipeline 34 further.

The pressure leading to the charging of the 4th convertor 48 can be at least 3500psig (24,233kPa), such as at least 4000psig (27,680kPa), such as at least 4500psig (31,128kPa).The temperature of the charging leading to the 4th convertor can be at least 90 DEG C, such as at least 95 DEG C. In the 4th convertor 48, the reaction of hydrogen and MGN is thermopositive reaction. Therefore, the temperature of the outflow logistics leaving the 4th convertor 48 can be higher at least 5 DEG C than the temperature of the streams entering the 4th convertor 48, such as at least 10 DEG C. The temperature of the streams leaving the 4th convertor 48 preferably should be no more than 200 DEG C, such as 190 DEG C, such as 180 DEG C. Citing, the streams leaving the 4th convertor 48 can have at 130 DEG C to the temperature within the scope of 180 DEG C and the pressure in 4100 to 4500psig (28,370 to 31,128kPa) scope.

Effluent from fourth stage convertor 48 arrives heat exchanger 60 through pipeline 58. Effluent from the 4th convertor can in the low temperature range to 30 DEG C to 60 DEG C of the pressure drop of 4100 to 4500psig (28,370 to 31,128kPa) in heat exchanger 60. Effluent through cooling passes pipeline 62 to product separation device 64 from heat exchanger 60 subsequently. There is flash distillation in product separation device 64. In product separation device 64, it is possible to be reduced to by the pressure of the effluent from the 4th convertor 48 in the scope of 450 to 500psig (3,204 to 3,549kPa), thus cause being separated of at least one liquid phase and at least one steam phase.

The liquid phase comprising MPMD from product separation device 64 arrives heat exchanger 60 through pipeline 66. Liquid phase can be heated to the temperature of about 65 DEG C to 85 DEG C in heat exchanger 60. The incoming flow entering ammonia recovery system 70 along pipeline 68 can have the temperature of 65 DEG C to 85 DEG C and the pressure of 465 to 480psig (3,307 to 3,411kPa). Streams in pipeline 68 can comprise 55wt% to 65wt% ammonia, 35wt% to 45wt%MPMD and be less than 1wt%, the hydrogen of such as 0.1wt% to 0.5wt%.

Ammonia recovery system 70 comprises recovery ammonia tower (not shown in figure 1) and condenser (not shown in figure 1). Recovery ammonia tower can have the bottom temp of 150 DEG C and the head temperature of 67 DEG C. Described tower can higher than air pressing operation. The crude product comprising MPMD obtains from ammonia tower bottom and leaves ammonia recovery system via pipeline 72. This crude product can comprise at least 90wt%MPMD. Crude product can be refined to remove impurity further.

Gas phase top material from recovery ammonia tower spreads in condenser, in described condenser, is formed and comprises the overhead product phase of ammonia and comprise the steam phase of hydrogen. Part overhead product can return recovery ammonia tower by backflow form mutually. Part overhead product can be transported at least one hold-up vessel mutually for storing. Part overhead product can also be recycled to hydrogenation as ammonia charging mutually. In FIG, this kind of recirculation of ammonia is represented to pipeline 2 from ammonia recovery system through pipeline 74 by ammonia.

From the gas phase comprising hydrogen and ammonia of product separation device 64 through pipeline 86, to gas recycle pump 88, to promote, hydrogen and ammonia flow through pipeline 18. Gas in pipeline 86 can comprise 92wt% to 96wt% hydrogen (H₂) and 4wt% to 8wt% ammonia (NH₃)��

Ammonia source, through pipeline 2 and ammonia pump 10, enters the hydrogen in pipeline 18/ammonia recycled matter stream via pipeline 12. Ammonia source can also comprise via the recycle of ammonia in pipeline 74 introduction pipe line 2. Sources of hydrogen also enters hydrogen gas compressor 14 through pipeline 4. Ammonia enters pipeline 18 from ammonia pump 10 through pipeline 12, and hydrogen enters pipeline 18 from hydrogen gas compressor through pipeline 16.The streams comprising ammonia and hydrogen in pipeline 18 carries out part heating in heat exchanger 20, and it is subsequently through pipeline 22 to convertor preheater 24. The ammonia through heating and hydrogen from preheater 24 pass a series of four convertors subsequently, are depicted as convertor 42,44,46 and 48 in FIG.

MGN feed source is from pipeline 28 feed-in dintrile pump 30. MGN charging is from dintrile pump 30 through pipeline 32 to pipeline 34. Part MGN charging can through pipeline 34 to ammonia feeding line 2. Part MGN charging can also be flowed 36 via side and be passed to pipeline 26 from pipeline 34 to introduce first stage convertor 42. Similarly, the fresh MGN charging of subordinate phase convertor 44 and phase III convertor 46 is led in side stream 38 and 40 offer. , as depicted in FIG. 1, in addition the fresh MGN charging in pipeline 34 is introduced in fourth stage convertor 48.

In optional embodiment, pipeline 76 comprises hydrogen and ammonia steam phase at least partially through the charging of unshowned pipeline in Fig. 1 as catalyst activation unit, described catalyst activation unit is used for by preparing catalyzer with hydrogen reducing ferric oxide. This streams can comprise 55wt% to 65wt% hydrogen (H₂) and 35wt% to 45wt% ammonia (NH₃)��

Example 2

This example is described through the embodiment forming catalyzer in the presence of ammonia with hydrogen reducing ferric oxide.

Referring to Fig. 2, from 100 supply of hydrogen of originating. In this example, sources of hydrogen 104 is not used. From the hydrogen of source 100 supply from Hydrogen Line, it is by transformation adsorption treatment purifying.

By the pressurized with hydrogen in source 100 to 200 to 400psig (1,480 to 2,859kPa), such as 250 to 350psig (1,825 to 2,515kPa), the such as pressure of 300psig (2,170kPa). The hydrogen from source 100 is made sequentially to arrive preheater 110 through pipeline 102 and pipeline 108. Hydrogen through heating arrives hydrogen/ammonia mixing tank 118 through pipeline 112. The ammonia charging leading to hydrogen/ammonia mixing tank 118 derives from ammonia source 114. Ammonia in source 114 is anhydrous liquid ammonia, is pressurized to 300 to 500psig (2,170 to 3,549kPa), such as 350 to 450psig (2,515 to 3,204kPa), the such as pressure of 400psig (2,859kPa). Ammonia charging enters hydrogen/ammonia mixing tank 118 via pipeline 116.

The liquefied ammonia of feed-in hydrogen/ammonia mixing tank 118 is vaporized in presence of hydrogen, forms gaseous hydrogen/ammonia mixture. This mixture can comprise 96mol% to 98mol%, such as 97mol% hydrogen; With 2mol% to 4mol%, such as 3mol% ammonia. Liquefied ammonia can at ambient temperature, such as, lower than at the temperature of 30 DEG C, introduced in hydrogen/ammonia mixing tank 118. Hydrogen is heated to by preheater 110 be enough to make ammonia in hydrogen/ammonia mixing tank 118 and hydrogen/ammonia mixing tank 118 downstream streams in keep the temperature of gaseous state. For example, the temperature of the hydrogen in pipeline 112 can be at least 120 DEG C, such as 120 DEG C to 140 DEG C, such as 130 DEG C. Leave hydrogen/ammonia mixing tank 118 and can be at least 30 DEG C, such as 30 DEG C to 50 DEG C, such as 40 DEG C to the temperature of the hydrogen/ammonia mixture of pipeline 120.

As shown in Figure 2, in two heating stepses, the gradual temperature of hydrogen/ammonia mixture rises to suitable temperature of reaction. In the first heating steps, mixture passes to pipeline 122 from pipeline 120 and enters heat exchanger 124. The temperature of the hydrogen/ammonia mixture leaving heat exchanger 124 via pipeline 126 can be such as at least 50 DEG C, such as 60 DEG C to 350 DEG C.Leaving the temperature that preheater 128 enters pipeline 130 and enter the hydrogen/ammonia mixture of catalyst activation unit 132 can be 375 DEG C to 425 DEG C, such as 385 DEG C to 415 DEG C, such as 400 DEG C. The pressure entering the hydrogen/ammonia mixture of catalyst activation unit 132 can be at least 25psig (274kPa), such as 50 to 200psig (446 to 1,480kPa), such as 120psig (929kPa).

In catalyst activation unit 132, ferric oxide and hydrogen reaction produce water (H₂O) as by product. In addition, ammonia (NH₃) occur some to decompose, produce hydrogen (H₂) and nitrogen (N₂). Therefore, the gaseous effluent leaving catalyst activation unit 132 and entering pipeline 134 comprises the mixture of hydrogen, ammonia, water and nitrogen. The composition of this gaseous mixture depends on the purity of the hydrogen loading catalyst activation unit at least in part, and can change based on the selection of this point and operational condition.

The reduction reaction occurred in catalyst activation unit 132 is thermo-negative reaction. The temperature of the effluent leaving catalyst activation unit 132 can be lower than the temperature of the charging leading to catalyst activation unit 132 at least 10 DEG C, such as low 15 DEG C to 40 DEG C, such as low 25 DEG C. The temperature leaving the effluent of catalyst activation unit 132 can be 300 DEG C to 450 DEG C, such as 350 DEG C to 425 DEG C, such as 360 DEG C to 400 DEG C, such as 375 DEG C. The pressure leaving the effluent of catalyst activation unit 132 can be at least 25psig (274kPa), such as 50 to 200psig (446 to 1,480kPa), such as 100psig (791kPa).

Reduce the temperature of the effluent from catalyst activation unit in two steps. In the first step, the temperature of this effluent by making described effluent by pipeline 134 and is partly reduced by heat exchanger 124. In this way it would be possible, to entering heat exchanger 124 via pipeline 122 and leave the hydrogen/ammonia mixture supply heat of heat exchanger 124 via pipeline 126. In the 2nd cooling step, the effluent from catalyst activation unit 132 through part cooling cools in water cooler 138. In this way it would be possible, by the decrease in temperature of effluent to the temperature being enough to allow to be separated in separator 142.

The effluent through cooling from catalyst activation unit 132 enters separator 142 from water cooler 138 through pipeline 140. In separator 142, the effluent from catalyst activation unit 132 is under atmospheric pressure separated into the liquid phase comprising ammonia and water and comprises the gas phase of hydrogen and ammonia. Reaching maximum to make the water yield in liquid phase and make to stay the water yield in the gas phase to drop to minimum, the effluent entering separator 142 can be cooled to 10 DEG C or lower by means of heat exchanger 124 and water cooler 138, the such as temperature of 5 DEG C or lower.

The water mixed with ammonia moves out from separator 142 via pipeline 148 with liquid form. Gas phase at least partially in separator 142 is moved out from separator via pipeline 144 to be recycled to catalytic activation unit 132. The temperature of the gas in pipeline 144 can be 10 DEG C or lower, such as 5 DEG C or lower, such as 2 DEG C. A part of gas phase in separator 142 can also be removed with purge stream form via pipeline 150. By taking out purification stream from the gas phase of separator 142, it is possible to make the accumulation of nitrogen in recirculation loop drop to minimum.

Gas phase for recirculation through pipeline 144 and passes compressor 146.In this way it would be possible, the pressure of the gaseous tension gas that is increased in pipeline 120 and 122.

Example 3

This example is described through brief interruption dintrile incoming flow to improve catalyst activity, and described dintrile incoming flow is led to for adiponitrile changes into convertor used in the method for hexamethylene-diamine (HMD).

By Fig. 4 to three elementary reaction methods shown in 7, adiponitrile hydrogenation forms hexamethylene-diamine. Pass in time, observe catalyst aging. Specifically, in order to maintain constant hexamethylene-diamine manufacture level, it may also be useful to lead to the constant feed rate of each in convertor 327,337,348, it is necessary to improve the temperature of the charging leading to each convertor. Specifically, in the process of about two weeks, the feeding temperature of the first convertor 327 is increased to 99.5 DEG C from 90 DEG C, and the feeding temperature of the 2nd convertor 337 is increased to 1041 DEG C from 95 DEG C, and the feeding temperature of the 3rd convertor 348 is increased to 156.3 DEG C from 141.5 DEG C.

Now, the dintrile incoming flow of each convertor is stopped. Specifically, close adiponitrile pump 306 and pump 303 and close and pipeline leads to these pumps and the suitable valve from these pumps. Gas circulating compressor 317, compression section 311 and ammonia pump 314 continuation operation. After about 0.5 hour, from convertor, move out of all extensible dintrile chargings and diamines product, and closed ammonia pump 314. In order to keep hydrogen recycle to pass through convertor, gas circulating compressor 317 continues to run. Under keeping pressure that convertor is in 2000psig to 5500psig (6996kPa to 38,022kPa), compression section 311 also continues to run. In order to the temperature of the charging by leading to the first converter inlet maintains 100 DEG C to 200 DEG C, in system, add heat via preheater 323.

Hydrogen recycle continues 4 to 12 hours.

Along with hydrogen stream continues, the activity of catalyzer, exactly, the activity of the catalyzer in last convertor 348 seems to make moderate progress. Without being bound by any theory, in theory, high pressure hydrogen likely can react with the iron catalyst of any oxidation and make reactivation of catalyst.

Interrupt after 4 to 12 hours, recover ammonia and adiponitrile charging. Recover after normal operating condition, the entrance and exit temperature of final convertor 348 2 DEG C to 5 DEG C compared to these decrease in temperature before interrupting in adiponitrile charging, though reach with interrupt before identical level of conversion time be also like this. The service temperature of this kind lower of final convertor 348 seems also to make the formation minimizing of hexamethylene imine (HMI) to reach 0.15%.

The temperature dependency that hexamethylene imine (HMI) is formed is very strong. For example, before adiponitrile charging is interrupted, the temperature in final convertor 348 can be enough high, so that rough hexamethylene-diamine (HMD) is containing 2.0wt% hexamethylene imine (HMI). When equivalent conversion, after adiponitrile charging is interrupted, the decrease in temperature in final convertor 348 so that rough hexamethylene-diamine (HMD) is containing 1.85wt% hexamethylene imine (HMI).

Interrupted by adiponitrile charging making aging catalyst part reactivate that catalyst life can be made to extend at least 1 or 2 day.

Claim used herein and term are considered as the change form of described the present invention. These claims are not limited to this kind of change form, but should be read as the whole scopes containing the present invention and being implied in this disclosure.

Claims

1., by dintrile changes into the method that diamines manufactures diamines, described method comprises following step:

B () makes hydrogen contact in each convertor of step (a) so that described dintrile and hydrogen reaction form described diamines with diamines;

C () makes the effluent comprising described diamines exit from each convertor;

D () passes the temperature improving the charging leading at least one convertor in time aging with compensate for catalyst;

F () flushes out remaining dintrile charging, ammonia and diamines product from the described convertor of step (e), maintain hydrogen stream through described convertor simultaneously; And

G () recovers the outflow logistics of described ammonia and dintrile incoming flow and the described convertor from step (f) entering in the described convertor of step (f), similar manufacture level before simultaneously maintaining step (d), and maintain the temperature of temperature lower than described charging before starting of the charging leading to described convertor in step (e) simultaneously.

2. method according to claim 1, wherein after step (g) starts, maintaining the similar manufacture level within the 10% of the manufacture level maintained before step (d), the temperature simultaneously maintaining the charging leading to described convertor in step (g) is lower than the temperature of described charging before starting in step (e).

3. method according to claim 1, wherein each convertor comprises the cylinder-shaped sleeve being filled with catalyst fixed bed vertical arrangement;

The bottom of wherein said cylinder-shaped sleeve comprises at least two outlet openings further;

The top of wherein said cylinder-shaped sleeve comprises the void space being placed in described catalyst fixed bed top; And

Wherein by the charging comprising dintrile, liquid state or supercritical ammine and hydrogen being introduced in the described void space above described catalyst bed, make described charging be downward through described catalyst bed and effluent is exited via the described outlet opening in the described bottom of described sleeve pipe, described charging is introduced in each convertor and effluent is exited from each convertor.

4. method according to claim 3, wherein each convertor comprises the vertical tube of vertically arrangement further, it extends up through the described bottom of described cylinder-shaped sleeve, through described fixing catalyst bed and extend to the described void space above the level attitude of described fixing catalyst bed in described cylinder-shaped sleeve;

Wherein said vertical tube is included in the entrance of the described bottom of described cylinder-shaped sleeve and at least one outlet in the region of the described void space of described sleeve pipe; And

Wherein step (a), (b) and (c) are undertaken by the method comprising following step:

I the charging comprising dintrile, liquefied ammonia and hydrogen is introduced in the described entrance of described vertical tube by ();

(ii) described charging is made upwards to flow through the described outlet of described vertical tube to described vertical tube;

(iii) the described catalyst bed that described charging flows downwards through in the annular space between described vertical tube and the vertical wall of described sleeve pipe is made; And

(iv) described effluent is made to exit via the described outlet opening in the described bottom of described sleeve pipe.

5. method according to claim 1, wherein dintrile is converted into diamines at least three convertors being connected in series;

Wherein effluent from the first convertor in described series passes to the 2nd convertor in described series, and passes to the 3rd convertor in described series from the effluent of described 2nd convertor in described series; And

Wherein in step (e), interrupt described dintrile and the ammonia incoming flow of all described convertors.

6. method according to claim 5, wherein described effluent from described first convertor cooled before passing to described 2nd convertor, and cooled before passing to described 3rd convertor from the described effluent of described 2nd convertor.

7. method according to claim 1, wherein in step (b), under the pressure in each convertor maintains the level of at least 4000psig (27,680kPa).

8. method according to claim 1, wherein said catalyzer is the ferric oxide of reduction form.

9. method according to claim 1, wherein said dintrile is adiponitrile and described diamines is hexamethylene-diamine.

10. method according to claim 1, wherein said dintrile is methyl cellosolve acetate glutaronitrile and described diamines is 2-methyl pentamethylene diamine.

11. methods according to claim 1, wherein pass the temperature in of at least one convertor of monitoring in time; And

Wherein when this temperature in is increased to predeterminated level in step (d) period, initial step (e).

12. methods according to claim 1, wherein pass the temperature out of at least one convertor of monitoring in time; And

Wherein when this temperature out is increased to predeterminated level in step (d) period, initial step (e).

13. methods according to claim 9, wherein pass the manufacture level of monitoring hexamethylene imine (HMI) in time; And

Wherein when the manufacture level of this hexamethylene imine (HMI) is increased to predeterminated level in step (d) period, initial step (e).

14. methods according to claim 13, wherein after the step (e) manufacture level of hexamethylene imine lower than the manufacture level of hexamethylene imine before starting in step (e).