CN106866429A

CN106866429A - Serialization catalytic hydrogenation is produced and catalyst regeneration device and method

Info

Publication number: CN106866429A
Application number: CN201710229325.0A
Authority: CN
Inventors: 国海光; 孙兵
Original assignee: SHANGHAI XUNKAI NEW MATERIAL TECHNOLOGY Co Ltd
Current assignee: SHANGHAI XUNKAI NEW MATERIAL TECHNOLOGY Co Ltd
Priority date: 2017-04-10
Filing date: 2017-04-10
Publication date: 2017-06-20
Anticipated expiration: 2037-04-10
Also published as: CN106866429B

Abstract

The invention discloses a kind of production of serialization catalytic hydrogenation and catalyst regeneration device, continuous production and reactor hydrogenation catalyst in-situ regeneration for realizing hydrogenation product；Section is hydrogenated with including being hydrogenated with section, catalyst regenerator section, fixed bed reactors by pipeline connection and closed melt zone, reactor；Reactor hydrogenation section includes two high-pressure hydrogenation reactors of parallel connection, catalyst regenerator section and wherein one high-pressure hydrogenation reactor composition catalyst original position regenerative system.The present invention can realize the continuous production of Automated condtrol hydrogenation product, and the in-situ regeneration treatment of reactor hydrogenation catalyst, so as to extend the use time of catalyst, reduce the loss of catalyst, shorten production procedure, reducing energy consumption, improve production efficiency can produce high-quality, hydrogenation product in high yield.The invention also discloses a kind of production of serialization catalytic hydrogenation and catalyst recovery process.

Description

Serialization catalytic hydrogenation is produced and catalyst regeneration device and method

Technical field

The present invention relates to a kind of chemical production device, and in particular to a kind of serialization catalytic hydrogenation production and catalyst regeneration Device.The invention further relates to a kind of production of serialization catalytic hydrogenation and catalyst recovery process.

Background technology

At present, catalytic hydrogenation production is substantially using batch tank reactor, or continuous tank reactor, Huo Zhegu Fixed bed reactor, or fluidized-bed reactor.

Batch tank reactor, its advantage is flexible operation, it is easy to convert different operating condition and product variety, it is adaptable to Small lot, multi items, reaction time production more long；Have the disadvantage the discontinuous production of interruption, the product per batch reaction Can be because being influenceed and there is fluctuation by operating.

Continuous tank reactor, its advantage can be achieved on continuous production, however it is necessary that compared with multiple reactor series connection or simultaneously Connection, is only applicable special reaction, for increasing or in complete mixing flow state response selectivity with trans time lengthening, side reaction Hydrogenation reaction not high.

The common feature of tank reactor is：Because catalyst is used in reactor, with increasing for access times, hydrogen Change the phenomenon that catalyst occurs activity decrease, cause selective reduction, side reaction to increase, it is impossible to meet production needs.It is solution Certainly the problem, typically all using regeneration treatment is carried out after catalyst is drawn off, makes its activation recovering.Chinese patent literature CN102658171B discloses a kind of renovation process of the catalyst that DSD acid is prepared for catalytic hydrogenation, will draw off catalyst and exists Regenerated carbon supported precious metal catalyst is carried out in tube furnace and reactor.

Fixed bed reactors, its advantage is operating process simple, and material and hydrogenation technique are easy to adjustment, can continuous metaplasia Produce, but have that reaction efficiency is low in itself, the big shortcoming of disposable loaded catalyst can not be solved very well simultaneously for hydrogenation reaction Certainly move heat problem.

O-chloraniline is the important intermediate of agricultural chemicals, medicine, spices, dyestuff, polyurethane industrial.The industrial adjacent chlorobenzene of production The method of amine carries out reduction reaction and obtains o-chloraniline with o-chloronitrobenzene as raw material.Due to iron powder reducing method, sodium sulfide reducing Method, hydrazine hydrate reduction method there are problems that it is with serious pollution be eliminated, the production technique that commonly uses of o-chloraniline uses bone at present Frame nickel is catalyst, adds desulfurization inhibitor, and in methyl alcohol or ethanol solution, catalytic hydrogenation o-chloronitrobenzene obtains adjacent chlorobenzene Amine.Due to the presence of course of reaction dechlorination, product quality decline is not only resulted in, yield is low, and dechlorination can also cause equipment corrosion, The problems such as catalyst poisoning.If addition solvent can also bring the recovery and environmental pollution of solvent in course of reaction, low boiling is molten Agent brings potential safety hazard, while increasing production cost.

Chinese patent literature CN103387498 discloses a kind of method and device of solvent-free production o-chloraniline, with neighbour Chloronitrobenzene is raw material, adds auxiliary agent 1 and anti-dechlorination inhibitor, the ammoniacal liquor of auxiliary agent 2 and catalyst platinum charcoal, controls the pH value of hydride It is 6~8, control pressure is 0.5~0.9MPa, 85~105 DEG C of temperature is passed through hydrogen successive reaction in reactor, after reaction Hydride collected in hydrogenation liquid bath by catalyst filter, catalyst carries out reactor weight after crossing filter by blowback Use again.

Chinese patent literature CN101333169 discloses a kind of production method of o-chloraniline, and o-nitrochlorobenzene is dissolved in alcohol In solvent in the presence of catalyst and auxiliary agent, reacted with hydrogen under 10~120 DEG C and 0.3~4.0MPa, course of reaction is company Continuous reaction, is connected using 1~6 reactor.Catalyst is Ni/Al₂O₃, Raney's nickel, Pt/C, Pd/C.

Chinese patent literature CN100436303 discloses a kind of preparation method of o-chloraniline, with o-chloronitrobenzene as former Material, in the presence of alcoholic solution and catalyst, reacts at 150~250 DEG C, and reaction post processing completely obtains o-chloraniline, is catalyzed Agent is Ru/C, amorphous state NiB, Ni-Fe-B, Ni-Co-B, and hydrogen is obtained by the way that solvent catalysis are cracked.

Chinese patent literature CN103664641 discloses a kind of method of solvent-free preparing o-chloroaniline by catalytic hydrogenation, with O-chloronitrobenzene is raw material, in the presence of a catalyst, is reacted with hydrogen under 70~120 DEG C and 0.5~5.0MPa pressure, reaction Process is hydrogenated with without solvent in reactor.

Chinese patent literature CN104098477 discloses a kind of o-nitrochlorobenzene continuous catalytic hydrogenation also original production neighbour chlorobenzene The device and method of amine, by o-nitrochlorobenzene, catalyst, the dechlorination inhibitor input good bed material of hydrogenation reactor cloth, uses nitrogen successively Gas and hydrogen are clean by system displacement, open inlet valve, are 1 by o-nitrochlorobenzene and dechlorination inhibitor mass ratio:0.001~ 0.005:0.001~0.005, hydrogen is passed through, carry out hydrogenation reaction, 60~100 DEG C of reaction temperature, 0.5~1.5MPa of pressure, hydrogen Change liquid and heat exchanger is initially entered by circulating pump, then by cross-flow filter, catalyst and part hydride and fresh feed one Rise into injector and go circulation, another part hydride is continuously produced, and o-chloraniline is obtained through subsequent treatment.

Chinese patent literature CN101774931 discloses a kind of method of preparing o-chloroaniline by catalytic hydrogenation, by adjacent nitro Chlorobenzene, ethyl acetate solution, dechlorination inhibitor and hydrogen are urged under 25~90 DEG C of temperature conditionss under catalyst action Change hydrogenation synthesizing reaction, using fixed bed reactors, with nickel alloy as catalyst, with neutral carrier catalyst carrier.

Chinese patent literature CN103664642 discloses the side that a kind of use microchannel reaction unit prepares o-chloraniline Method, reaction use microchannel reaction unit, o-chloronitrobenzene, solvent and catalyst by the way of slurry feed, with 50~150 DEG C and the pressure of 0.5~1.2MPa under with hydrogen reaction, obtain o-chloraniline.

Chinese patent literature CN103360267 discloses a kind of Continuous Liquid Phase catalytic hydrogenating reduction production o-chloraniline side Method, hydrogenation reaction is reacted using multi-floating bodies, and matches somebody with somebody heat exchanger and injector on 1# hydrogenation kettles, and partial reaction material is by following Ring pump is circulated between heat exchanger, injector and 1# hydrogenation kettle, o-nitrochlorobenzene is fully converted into o-chloraniline, and Suspension separator always is installed behind every hydrogenation reaction kettle, the catalyst in hydride is isolated, the catalyst isolated is again Corresponding hydrogenation kettle is returned to by circulating pump to recycle.

Chinese patent literature 201610903803.7 discloses a kind of catalytic hydrogenation continuous production device and production method, Connected using reactor and fixed bed, centre is separated and return mechanism using catalyst, it is ensured that continuous prodution, but cannot be real Existing catalyst on-line regeneration, catalyst is separated and returning equipment is more complicated.

In sum, the production technology of existing o-chloraniline and device are produced and there is many defects, many kettle strings the need for having Connection, complicated catalyst separation equipment the need for having, purification apparatus, pyroreaction the need for having after being hydrogenated with the need for having, although Multi-floating bodies can realize continuous production, but because reactor is complete mixed reaction, and cause reaction time mistake by multi-floating bodies It is long, reduce product yield, quality variation.The unlimited system or intermediate steps of hydrogenation process closed can all can not be caused Injury to body and the pollution to environment, need to draw off regeneration treatment after still reaction fine catalyst inactivation, cause catalysis The loss and environmental pollution of agent, while reduce production capacity, simultaneously because o-chloronitrobenzene hydrogenation has dechlorination phenomenon, except making Into outside catalyst poisoning, equipment corrosion, production cost can be also caused to increase, equipment safety hidden danger increases.If added organic molten Agent is reacted, and can cause separation and purification and the loss problem of solvent, increases production cost and operational hazards.Therefore it is urgent A kind of new continuous catalytic hydrogenation production of design and its catalyst on-line regeneration technique and device are needed, to overcome existing production The deficiency of technique and device.

The content of the invention

The technical problems to be solved by the invention are to provide a kind of serialization catalytic hydrogenation production and catalyst regeneration device, It can realize that the Automated condtrol of hydrogenation product is continuously produced, so that improve production efficiency；Can realize that reactor adds simultaneously The online in-situ regeneration of hydrogen catalyst, extends catalyst service life.

In order to solve the above technical problems, the technology of serialization catalytic hydrogenation production of the present invention and catalyst regeneration device is solved Scheme is：

Continuous production and reactor hydrogenation catalyst in-situ regeneration for realizing hydrogenation product；Including being connected by pipeline And closed melt zone 1, reactor hydrogenation section 2, catalyst regenerator section 3, fixed bed reactors hydrogenation section 4；Reactor is hydrogenated with section 2 Including two high-pressure hydrogenation reactors of parallel connection, catalyst regenerator section 3 constitutes catalyst with wherein one high-pressure hydrogenation reactor In-situ regeneration system；

Raw material is melted in melt zone 1；Fused raw material alternately enters two high-pressure hydrogenation reactors that reactor is hydrogenated with section 2, There is hydrogenation reaction, material after being hydrogenated with hydrogen in the presence of hydrogenation catalyst；Material is by filtering, filtrate after hydrogenation Section 4 is hydrogenated with into fixed bed reactors, is reacted under the catalytic action of fixed bed catalyst 404 with hydrogen, hydrogenated Product；

Hydrogenation reaction and catalyst regeneration process staggeredly are carried out in two high-pressure hydrogenation reactors, when the first high-pressure hydrogenation is anti- When answering kettle 201 and carrying out hydrogenation reaction, the second high-pressure hydrogenation reactor 211 is in situ with the catalyst that catalyst regenerator section 3 is constituted Regenerative system carries out catalyst regeneration process, makes hydrogenation catalyst in-situ regeneration in the second high-pressure hydrogenation reactor 211；It is same Hydrogenation reaction in high-pressure hydrogenation reactor is staggeredly carried out with regeneration treatment, to ensure the continuity of reaction；Whole material is in Air-tight state, material realizes automatic transport.

The melt zone 1 includes the first closed container 101 and the second closed container 102, and the first closed container 101 is offered Material inlet, the first closed container 101 connects the second closed container 102 by feedstock transportation pipeline 106；Material is introduced into first Closed container 101, the second closed container 102 is entered after the melting of the first closed container 101 by feedstock transportation pipeline 106；The One closed container 101 connects the second closed container 102 by pressure-equalizing line 103, when pressure-equalizing line 103 is connected, Realize that the first closed container 101 and the second closed container 102 are isobaric；The connection feedstock transportation house steward's of second closed container 102 is defeated Enter end, the output end of feedstock transportation house steward connects the first feed inlet lines and the second feed inlet lines by triple valve 105 Input, the of the output end difference coupled reaction kettle hydrogenation section 2 of the first feed inlet lines and the second feed inlet lines One high-pressure hydrogenation reactor 201 and the second high-pressure hydrogenation reactor 211；Feedstock transportation pump 104 is provided with feedstock transportation house steward； By the switching of triple valve 105, fused raw material can be made to interlock into the first high-pressure hydrogenation reactor 201 and the second high-pressure hydrogenation Reactor 211.The feedstock transportation pump 104 is measuring pump.

The reactor hydrogenation section 2 includes that the first high-pressure hydrogenation reactor 201 and the second high-pressure hydrogenation parallel with one another is anti- Answer kettle 211；The first high-pressure hydrogenation reactor 201 connects the first feed inlet lines, the first hydrogen inlet pipeline 205, the One nitrogen inlet pipeline 203, the first catalyst or deionized water suction line 206, the first dead catalyst outlet line 208, One catalyst regenerated liquid suction line, the first reactor outlet line；First hydrogen inlet pipeline 205 and the first nitrogen inlet tube Line 203 is passed through the top of the first high-pressure hydrogenation reactor 201, and the first catalyst or deionized water suction line 206 and first are useless Catalyst outlet pipeline 208 is passed through the bottom of the first high-pressure hydrogenation reactor 201；First reactor outlet line passes through triple valve 309 the first catalyst regeneration liquid waste of connection outlets or blowback nitrogen inlet pipeline 310 and the first hydrogenated filtrate pipeline 410, threeway Valve 309 can enter to the outlet of the first catalyst regeneration liquid waste or blowback nitrogen inlet pipeline 310 and the first hydrogenated filtrate pipeline 410 Row switching；First catalyst or the dead catalyst outlet line 208 of deionized water suction line 206 and first pass through triple valve 207 Switch over；First nitrogen inlet pipeline 203 and the first hydrogen inlet pipeline 205 are switched over by triple valve 204；First is high Pressure hydrogenation reaction kettle 201 is built with the first built-in type filter 202；The connection of second high-pressure hydrogenation reactor 211 second is former Material suction line, the second hydrogen inlet pipeline 215, the second nitrogen inlet pipeline 213, the second catalyst or deionized water inlet tube Line 216, the second dead catalyst outlet line 218, the second catalyst regenerated liquid suction line, the second reactor outlet line；The Two hydrogen suction lines 215 and the second nitrogen inlet pipeline 213 are passed through the top of the second high-pressure hydrogenation reactor 211, and second urges Agent or the dead catalyst outlet line 218 of deionized water suction line 216 and second are passed through the second high-pressure hydrogenation reactor 211 Bottom；Second reactor outlet line connects the second catalyst regeneration liquid waste and exports or blowback nitrogen inlet by triple valve 311 The hydrogenated filtrate pipeline 409 of pipeline 312 and second, triple valve 311 can be to the outlet of the second catalyst regeneration liquid waste or blowback nitrogen The hydrogenated filtrate pipeline 409 of suction line 312 and second is switched over；Second catalyst or deionized water suction line 216 and Two dead catalyst outlet lines 218 are switched over by triple valve 217；Second nitrogen inlet pipeline 213 and the second hydrogen inlet Pipeline 215 is switched over by triple valve 214；Second high-pressure hydrogenation reactor 211 is built with the second built-in type filter 212.

First built-in type filter 202 is high technology ceramics filtration core or precision metallic sintered filter core；In described second Formula filter 212 is put for high technology ceramics filtration core or precision metallic sintered filter core.

The first high-pressure hydrogenation reactor 201 and/or the second high-pressure hydrogenation reactor 211 equipped with temperature monitoring, One or more in pressure detector, automatic control heating device and cooling device and agitating device.

The first high-pressure hydrogenation reactor 201 and/or the second high-pressure hydrogenation reactor 211 use magnetic agitation or machinery Stirring, agitating mode is self-priming stirring.

The catalyst regenerator section 3 includes at least four regeneration liquid storage tanks 305,306,307,308 in parallel, regenerated liquid storage Tank 305,306,307,308 realizes switching by triple valve 303 and four-way valve 304, and by regenerated liquid delivery pump 302 and threeway The switching effect of valve 301 is transported to the first high-pressure hydrogenation reactor 201 or the second high-pressure hydrogenation reactor 211.The regenerated liquid Delivery pump 302 is measuring pump.

The fixed bed reactors hydrogenation section 4 includes fixed bed reactors 402, condenser 405, gas-liquid separator 406；Gu The top of fixed bed reactor 402 is provided with gas-liquid distributor 403, and the bed of fixed bed catalyst 404 is in fixed bed reactors 402 Flat-temperature zone；The input port of fixed bed reactors 402 connects the first of the first high-pressure hydrogenation reactor 201 by Location Detection of Medium Transportation Pipeline Second hydrogenated filtrate pipeline 409 of the high-pressure hydrogenation reactor 211 of hydrogenated filtrate pipeline 410 and second, the first hydrogenated filtrate pipeline 410 and second hydrogenated filtrate pipeline 409 Location Detection of Medium Transportation Pipeline is connected by triple valve 411；Thing is provided with Location Detection of Medium Transportation Pipeline Material conveying pump 401；Material from the first high-pressure hydrogenation reactor 201 or the second high-pressure hydrogenation reactor 211 passes through triple valve 411 switching is realized alternately entering fixed bed reactors 402；The delivery outlet of fixed bed reactors 402 connects the defeated of condenser 405 Entrance, the delivery outlet connection gas-liquid separator 406 of condenser 405；Gas-liquid separator 406 connects hydrogen pipeloop, and hydrogen is followed Hydrogen gas circulating pump 407 is provided with endless tube line；Fixed bed reactors 402 connect hydrogen inlet manifold line, hydrogen inlet manifold line and hydrogen Gas pipeloop connects outside constant pressure hydrogen gas lines 408 jointly.The material-handling pump 401 is measuring pump.

The present invention also provides a kind of serialization catalytic hydrogenation production and catalyst recovery process, in closed continuous device Realize continuous production and the reactor hydrogenation catalyst in-situ regeneration of hydrogenation product；Its technical solution is, including following step Suddenly：

Step S1, melting step：First by the pressure-equalizing pipe between the first closed container 101 and the second closed container 102 Line 103 and feedstock transportation pipeline 106 are cut off, and solid material is added in the first closed container 101, will by automatic control heating system Solid material heating melting；

Then pressure-equalizing line 103 is connected with feedstock transportation pipeline 106, pressure-equalizing line 103 makes first closed 101 and second closed container of container 102 is isobaric；Fused raw material enters the second closed container 102 through feedstock transportation pipeline 106；

Fused raw material is delivered to by the first high-pressure hydrogenation reactor 201 or the second high-pressure hydrogenation by feedstock transportation pump 104 Reactor 211；Two switchings of high-pressure hydrogenation reactor are realized by triple valve 105；

The temperature control of the first closed container 101 and the second closed container 102 is at 50~150 DEG C in the step S1.

Step S2, reactor hydrogenation step：Fresh hydrogenation catalyst passes through the first catalyst or deionized water suction line 206 are added in the first high-pressure hydrogenation reactor 201；In the presence of hydrogenation catalyst, the o-chloronitrobenzene of melting with come from There is hydrogenation reaction, thing after being hydrogenated with the first high-pressure hydrogenation reactor 201 in the hydrogen of the first hydrogen inlet pipeline 205 Material；

Material is by after the built-in type filter 202 of the bottom of the first high-pressure hydrogenation reactor 201, obtaining hydrogenation filter after hydrogenation Liquid is discharged, by the switching of triple valve 309, by being pumped into fixed bed hydrogenation section 4；

Or, fresh hydrogenation catalyst is added to the second high pressure by the second catalyst or deionized water suction line 216 In hydrogenation reaction kettle 211；In the presence of hydrogenation catalyst, the o-chloronitrobenzene of melting with come from the second hydrogen inlet pipeline There is hydrogenation reaction, material after being hydrogenated with the second high-pressure hydrogenation reactor 211 in 215 hydrogen；

Material is by after the built-in type filter 212 of the bottom of the second high-pressure hydrogenation reactor 211, obtaining hydrogenation filter after hydrogenation Liquid is discharged, by the switching of triple valve 311, by being pumped into fixed bed hydrogenation section 4；

50~100 DEG C of the temperature of hydrogenation reaction in the step S2,0.5~1.5MPa of pressure, mixing speed 600~ 1300r/min, it is self-priming stirring to stir.

Hydrogenation catalyst in the step S2 is loaded catalyst；The composition of the hydrogenation catalyst includes activearm Point, auxiliary agent and carrier；Active component is one or more in Pt, Pd, Rh, Ru, Ir, Ni；Auxiliary agent be Na, K, Mg, Fe, Sn, One or more in Ca, Ba, Cr, Mn, Mo, Zn, Co, rare earth element；Carrier is activated carbon, modified activated carbon, aluminum oxide, changes One or more in property aluminum oxide, silica, molecular sieve.

Preferably, the hydrogenation catalyst in the step S2 is powdered palladium charcoal, ruthenium charcoal, platinum charcoal, rhodium charcoal, the platinum containing auxiliary agent One or more in charcoal, the charcoal of palladium containing auxiliary agent, the charcoal of ruthenium containing auxiliary agent, the charcoal of rhodium containing auxiliary agent.

Preferably, the hydrogenation catalyst in the step S2 is platinum carbon catalyst containing auxiliary agent；The auxiliary agent is iron, tin, molybdenum In one or more, the weight percentage of auxiliary agent is 0.1~5%, and the platinum weight percentage of platinum charcoal is 1~5%.

Step S3, process catalyst regeneration step：When catalyst inactivation occurs in reaction in the first high-pressure hydrogenation reactor 201, then Stop material entering, material is reacted into the second high-pressure hydrogenation reactor 211 by the switching of triple valve 105；Treat After material is discharged totally through built-in type filter 202 after hydrogenation in one high-pressure hydrogenation reactor 201, by regenerated liquid delivery pump 302 squeeze into the first high-pressure hydrogenation reactor 201 regenerated liquid, and regenerated liquid is to the hydrogenation in the first high-pressure hydrogenation reactor 201 Catalyst carries out regeneration treatment；

Waste liquid is by after the filtering of the built-in type filter 202 of the bottom of the first high-pressure hydrogenation reactor 201 after regeneration, from One catalyst regeneration liquid waste is exported or blowback nitrogen inlet pipeline 310 is discharged；

Catalyst and deionized water suction line 206 that catalyst after regeneration passes through the first high-pressure hydrogenation reactor 201 Squeeze into deionized water to be washed, cleaning solution from the first catalyst regeneration liquid waste by after the filtering of built-in type filter 202, going out Mouth or blowback nitrogen inlet pipeline 310 are discharged；

The catalyst of the surface attachment of built-in type filter 202 carries out blowback stripping by blowback nitrogen；By the first catalyst Regeneration liquid waste is exported or the input blowback nitrogen of blowback nitrogen inlet pipeline 310, and the catalyst to the attachment of filter 202 is carried out instead Blow；

The regeneration treating method of the hydrogenation catalyst in the second high-pressure hydrogenation reactor 211 and the first high-pressure hydrogenation reactor 201 is identical；

Hydrogenation reaction and catalyst regeneration process staggeredly are carried out in two high-pressure hydrogenation reactors, when the first high-pressure hydrogenation is anti- When answering kettle 201 and carrying out hydrogenation reaction, the second high-pressure hydrogenation reactor 211 is in situ with the catalyst that catalyst regenerator section 3 is constituted Regenerative system carries out catalyst regeneration process, makes hydrogenation catalyst in-situ regeneration in the second high-pressure hydrogenation reactor 211；It is same Hydrogenation reaction in high-pressure hydrogenation reactor is staggeredly carried out with regeneration treatment；

600~1200 revs/min of the mixing speed of the catalyst regeneration process in the step S3,30~90 DEG C of temperature.

Regenerated liquid in the step S3 regenerate liquid storage tank 305,306,307,308 at four in one or more in enter Row selection；Built with aqueous alkali, alkali is inorganic base to first regeneration liquid storage tank 305, and mass concentration is 1%~20%, inorganic base For one or more in NaOH, potassium hydroxide, sodium carbonate, sodium acid carbonate, ammoniacal liquor；Second regeneration liquid storage tank 306 built with Organic solvent, organic solvent includes alcohols solvent, esters solvent, alkane solvents, aromatic solvents；The alcohols solvent is first One or more in alcohol, ethanol, isopropanol, butanol, the esters solvent is the one kind or many in ethyl acetate, butyl acetate Kind, the alkane solvents are that one or more in hexamethylene, n-hexane, heptane, octane, the aromatic solvents are benzene, first One or more in benzene, dimethylbenzene；Built with reducing agent aqueous solution, the reducing agent is hydration to 3rd regeneration liquid storage tank 307 One or more in hydrazine, formaldehyde, formic acid, sodium formate, potassium borohydride, sodium borohydride；The reducing agent aqueous solution weight percent Concentration is 1~10%；4th regeneration liquid storage tank 308 built with acidic aqueous solution, it is described acid for sulfuric acid, hydrochloric acid, nitric acid, acetic acid, One or more in phosphoric acid, perchloric acid, mass percentage concentration is 0.5~10%.

Step S4, fixed bed reaction step：Material-handling pump 401 will be from the first high-pressure hydrogenation reactor 201 or the second The hydrogenated filtrate of high-pressure hydrogenation reactor 211 squeezes into the top of fixed bed reactors 402, and fixed bed reactors 402 are built with solid Bed catalyst 404；Be input into hydrogen in fixed bed reactors 402 by outside constant pressure hydrogen gas lines 408, and hydrogenated filtrate exists with hydrogen Reacted under the catalytic action of fixed bed catalyst 404, obtained hydrogenation reaction product；

Hydrogenation reaction product passes sequentially through condenser 405 and gas-liquid separator 406, by condensation and gas-liquid separation, obtains Hydrogenation product；

Hydrogen is circulated by hydrogen gas circulating pump 407, and supplements consumed hydrogen by outside constant pressure hydrogen gas lines 408 Gas.

Reaction temperature in the step S4 in fixed bed reactors 402 is controlled in 40~90 DEG C, 0.5~1MPa of pressure.

Fixed bed catalyst 404 is loaded catalyst in the step S4, and the composition of fixed bed catalyst 404 includes living Property component, auxiliary agent and carrier；Active component is one or more in Pt, Pd, Rh, Ru, Ir, Ni；Auxiliary agent be Na, K, Mg, Fe, One or more in Sn, Ca, Ba, Cr, Mn, Mo, Zn, Co, rare earth element；Carrier is activated carbon, modified activated carbon, oxidation One or more in aluminium, modified aluminas, silica, molecular sieve.

Preferably, fixed bed catalyst 404 is the one kind in graininess platinum charcoal, ruthenium charcoal, palladium charcoal, rhodium charcoal in the step S4 Or it is various.

Preferably, fixed bed catalyst 404 is the platinum charcoal that particulate supported type catalyst contains auxiliary agent in the step S4, Auxiliary agent be iron, tin, one or more of molybdenum, the weight percentage of auxiliary agent is 0.1~5%, and the platinum load capacity of platinum charcoal is weight Percentage composition 0.3~3%.

The hydrogenation product is o-chloraniline；The catalyst recovery process is that the reactor hydrogenation powder charcoal of platinum containing auxiliary agent is urged The in situ regeneration method of agent.

What the present invention can reach has the technical effect that：

The present invention is staggeredly hydrogenated with using the reactors of two parallel connections, one in continuously hydrogen adding, one with catalyst again in addition Raw section constitutes catalyst regeneration system, the in-situ regeneration of reactor hydrogenation catalyst is realized, so as to extend making for hydrogenation catalyst Use the time.

The present invention can realize the continuous production of Automated condtrol hydrogenation product, and reactor hydrogenation catalyst original position Regeneration is processed such that it is able to extend the use time of catalyst, reduces the loss of catalyst, shortens production procedure, reducing energy consumption, Improve production efficiency, can produce high-quality, hydrogenation product in high yield.Meanwhile, continuous prodution process of the invention is entirely close Close, operating environment is excellent, the harm and the pollution to environment to the person can be reduced.

Brief description of the drawings

It should be understood by those skilled in the art that following explanation is only schematically to illustrate principle of the invention, the principle Can apply in many ways, to realize many different alternative embodiments.These explanations are only used for showing religion of the invention Lead the General Principle of content, it is not intended to which limitation is in the design of this disclosed invention.

The accompanying drawing for being incorporated in the present specification and constituting the part of this specification shows embodiments of the present invention, and And be used to explain principle of the invention together with the detailed description of general description and drawings below above.

The present invention is further detailed explanation with reference to the accompanying drawings and detailed description：

Fig. 1 is the schematic diagram of serialization catalytic hydrogenation production of the present invention and catalyst regeneration device；

Fig. 2 is the flow chart of serialization catalytic hydrogenation production of the present invention and catalyst recovery process.

Description of reference numerals in figure：

1 is melt zone, and 2 is that reactor is hydrogenated with section,

3 is catalyst regenerator section, and 4 is that fixed bed reactors are hydrogenated with section,

101 is the first closed container, and 102 is the second closed container,

103 is pressure-equalizing line, and 104 is feedstock transportation pump,

105 is triple valve, and 106 is feedstock transportation pipeline,

201 is the first high-pressure hydrogenation reactor, and 202 is the first built-in type filter,

203 is the first nitrogen inlet pipeline, and 204 is triple valve,

205 is the first hydrogen inlet pipeline,

206 be the first catalyst or deionized water suction line,

207 is triple valve, and 208 is the first dead catalyst outlet line,

211 is the second high-pressure hydrogenation reactor, and 212 is the second built-in type filter,

213 is the second nitrogen inlet pipeline, and 214 is triple valve,

215 is the second hydrogen inlet pipeline,

216 be the second catalyst or deionized water suction line,

217 is triple valve, and 218 is the second dead catalyst outlet line,

301 is triple valve, and 302 is regenerated liquid delivery pump,

303 is triple valve, and 304 is four-way valve,

305 is the first regeneration liquid storage tank, and 306 is the second regeneration liquid storage tank,

307 is the 3rd regeneration liquid storage tank, and 308 is the 4th regeneration liquid storage tank,

309 is triple valve,

310 is that the first catalyst regeneration liquid waste is exported or blowback nitrogen inlet pipeline,

311 is triple valve,

312 is that the second catalyst regeneration liquid waste is exported or blowback nitrogen inlet pipeline,

401 is material-handling pump, and 402 is fixed bed reactors,

403 is gas-liquid distributor, and 404 is fixed bed catalyst,

405 is condenser, and 406 is gas-liquid separator,

407 is hydrogen gas circulating pump, and 408 is outside constant pressure hydrogen gas lines,

409 is the first hydrogenated filtrate pipeline, and 410 is the second hydrogenated filtrate pipeline,

411 is triple valve.

Specific embodiment

To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, below in conjunction with the embodiment of the present invention Accompanying drawing, the technical scheme to the embodiment of the present invention is clearly and completely described.Obviously, described embodiment is this hair Bright a part of embodiment, rather than whole embodiments.Based on described embodiments of the invention, ordinary skill The every other embodiment that personnel are obtained on the premise of without creative work, belongs to the scope of protection of the invention.Remove Non- other definition, technical term used herein or scientific terminology are should be in art of the present invention with general technical ability The ordinary meaning that personage is understood." first " used herein, " second " and similar word be not offered as any order, Quantity or importance, and be used only to distinguish different parts." including " etc. before similar word means the word occur The element or object in face cover the element or object that appear in the word presented hereinafter and its equivalent, and are not excluded for other elements Or object.

As shown in figure 1, serialization catalytic hydrogenation production of the present invention and catalyst regeneration device, for realizing with adjacent chlorine nitro The continuous production of benzene preparing o-chloroaniline by catalytic hydrogenation and reactor hydrogenation catalyst in-situ regeneration；Including by pipeline connect and Closed melt zone 1, reactor hydrogenation section 2, catalyst regenerator section 3, fixed bed reactors hydrogenation section 4；Reactor hydrogenation section 2 is wrapped Include two high-pressure hydrogenation reactors of parallel connection, catalyst regenerator section 3 and wherein one high-pressure hydrogenation reactor composition catalysagen Position regenerative system；

Raw material o-chloronitrobenzene is melted in melt zone 1；Two high pressures that fused raw material alternately enters reactor hydrogenation section 2 add , there is hydrogenation reaction, material after being hydrogenated with hydrogen in the presence of hydrogenation catalyst in hydrogen reactor；Material passes through after hydrogenation Filtering, filtrate enters fixed bed reactors and is hydrogenated with section 4, is reacted under the catalytic action of fixed bed catalyst 404 with hydrogen, Obtain hydrogenation product o-chloraniline；

Melt zone 1 includes the first closed container 101 and the second closed container 102, and the top of the first closed container 101 opens up There is material inlet, the bottom of the first closed container 101 connects the top of the second closed container 102 by feedstock transportation pipeline 106； Material is introduced into the first closed container 101, and second is entered by feedstock transportation pipeline 106 after the melting of the first closed container 101 Closed container 102；

The top of the first closed container 101 connects the top of the second closed container 102 by pressure-equalizing line 103, when When pressure-equalizing line 103 is connected, realize that the first closed container 101 and the second closed container 102 are isobaric；

First closed container 101 and the second closed container 102 can use automatic temperature control heating.

Reactor hydrogenation section 2 includes the first high-pressure hydrogenation reactor 201 and the second high-pressure hydrogenation reactor parallel with one another 211；

The bottom of the second closed container 102 connects the input of feedstock transportation house steward, and the output end of feedstock transportation house steward is led to Cross the input that triple valve 105 connects the first feed inlet lines and the second feed inlet lines, the first feed inlet lines and First high-pressure hydrogenation reactor 201 and second of the output end difference coupled reaction kettle hydrogenation section 2 of the second feed inlet lines is high Pressure hydrogenation reaction kettle 211；Feedstock transportation pump 104 is provided with feedstock transportation house steward, feedstock transportation pump 104 is preferably measuring pump； By the switching of triple valve 105, fused raw material can be made to interlock into the first high-pressure hydrogenation reactor 201 and the second high-pressure hydrogenation Reactor 211；

First high-pressure hydrogenation reactor 201 connects the first feed inlet lines, the first hydrogen inlet pipeline 205, the first nitrogen Gas suction line 203, the first catalyst or deionized water suction line 206, the first dead catalyst outlet line 208, first are urged Agent regenerated liquid suction line, the first reaction mass filtrate (liquid pipeline, the outlet of the first catalyst regeneration liquid waste or blowback nitrogen Suction line 310；

First hydrogen inlet pipeline 205 and the first nitrogen inlet pipeline 203 are passed through the upper of the first high-pressure hydrogenation reactor 201 It is anti-that portion, the first catalyst or the dead catalyst outlet line 208 of deionized water suction line 206 and first are passed through the first high-pressure hydrogenation Answer the bottom of kettle 201；

First reactor outlet line connects the outlet of the first catalyst regeneration liquid waste by triple valve 309 or blowback nitrogen enters The mouth hydrogenated filtrate pipeline 410 of pipeline 310 and first, triple valve 309 can be to the outlet of the first catalyst regeneration liquid waste or blowback nitrogen The hydrogenated filtrate pipeline 410 of gas suction line 310 and first is switched over；

First catalyst or the dead catalyst outlet line 208 of deionized water suction line 206 and first pass through triple valve 207 Switch over；First nitrogen inlet pipeline 203 and the first hydrogen inlet pipeline 205 are switched over by triple valve 204；

The bottom of the first high-pressure hydrogenation reactor 201 is equipped with the first built-in type filter 202, the first built-in type filter 202 can be high technology ceramics filtration core or precision metallic sintered filter core；

Material is by after the built-in type filter 202 of the bottom of the first high-pressure hydrogenation reactor 201, obtaining hydrogenation filter after hydrogenation Liquid is discharged, by the switching of triple valve 309, by being pumped into fixed bed hydrogenation section 4；It is high that catalyst regenerated liquid is passed through first Press hydrogenation reaction kettle 201 top, after regeneration waste liquid by the bottom of the first high-pressure hydrogenation reactor 201 built-in type filter After 202 filtering, discharged from the outlet of the first catalyst regeneration liquid waste or blowback nitrogen inlet pipeline 310；

The catalyst of the surface attachment of built-in type filter 202 carries out blowback stripping by blowback nitrogen；By the first catalyst Regeneration liquid waste is exported or the input blowback nitrogen of blowback nitrogen inlet pipeline 310, and the catalyst of the attachment of filter 202 can be carried out Blowback；

Second high-pressure hydrogenation reactor 211 connects the second feed inlet lines, the second hydrogen inlet pipeline 215, the second nitrogen Gas suction line 213, the second catalyst or deionized water suction line 216, the second dead catalyst outlet line 218, second are urged Agent regenerated liquid suction line, the second reaction mass filtrate (liquid pipeline, the outlet of the second catalyst regeneration liquid waste or blowback nitrogen Suction line 312；

Second hydrogen inlet pipeline 215 and the second nitrogen inlet pipeline 213 are passed through the upper of the second high-pressure hydrogenation reactor 211 It is anti-that portion, the second catalyst or the dead catalyst outlet line 218 of deionized water suction line 216 and second are passed through the second high-pressure hydrogenation Answer the bottom of kettle 211；

Second reactor outlet line connects the outlet of the second catalyst regeneration liquid waste by triple valve 311 or blowback nitrogen enters The mouth hydrogenated filtrate pipeline 409 of pipeline 312 and second, triple valve 311 can be to the outlet of the second catalyst regeneration liquid waste or blowback nitrogen The hydrogenated filtrate pipeline 409 of gas suction line 312 and second is switched over；

Second catalyst or the dead catalyst outlet line 218 of deionized water suction line 216 and second pass through triple valve 217 Switch over；Second nitrogen inlet pipeline 213 and the second hydrogen inlet pipeline 215 are switched over by triple valve 214；

, built with the second built-in type filter 212, the second built-in type filter 212 can for second high-pressure hydrogenation reactor 211 Think high technology ceramics filtration core or precision metallic sintered filter core；

First hydrogen inlet pipeline 205 and the second hydrogen inlet pipeline 215 are respectively equipped with self-measuring device, and using outer Portion's constant pressure enters；All gateways are equipped with valve；The pipeline of one-way flow is provided with check valve；Into the raw material and again of reactor Raw liquid is realized controlling by measuring pump；

First high-pressure hydrogenation reactor 201 and the second high-pressure hydrogenation reactor 211 may be equipped with temperature monitoring, pressure One or more in detector, automatic control heating device and cooling device and agitating device；

First high-pressure hydrogenation reactor 201 and the second high-pressure hydrogenation reactor 211 use magnetic agitation or mechanical agitation, stir Mode is mixed for self-priming stirring.

Material is by after the built-in type filter 212 of the bottom of the second high-pressure hydrogenation reactor 211, obtaining hydrogenation filter after hydrogenation Liquid is discharged, by the switching of triple valve 311, by being pumped into fixed bed hydrogenation section 4；It is high that catalyst regenerated liquid is passed through second Press hydrogenation reaction kettle 211 top, after regeneration waste liquid by the bottom of the second high-pressure hydrogenation reactor 211 built-in type filter After 212 filtering, discharged from the outlet of the second catalyst regeneration liquid waste or blowback nitrogen inlet pipeline 312；

The catalyst of the surface attachment of built-in type filter 212 carries out blowback stripping by blowback nitrogen；By the second catalyst Regeneration liquid waste is exported or the input blowback nitrogen of blowback nitrogen inlet pipeline 312, and the catalyst of the attachment of filter 212 can be carried out Blowback.

Catalyst regenerator section 3 includes regeneration liquid storage tank 305,306,307,308 in parallel, regeneration liquid storage tank 305,306, 307th, the regenerated liquid in 308 realizes switching by triple valve 303 and four-way valve 304, and by regenerated liquid delivery pump 302 and threeway The switching effect of valve 301 is transported to the first high-pressure hydrogenation reactor 201 or the second high-pressure hydrogenation reactor 211；Regenerated liquid is conveyed Pump 302 is preferably measuring pump；

When one of two high-pressure hydrogenation reactors, such as the second high-pressure hydrogenation reactor 211 is used as catalyst treatment During kettle, regenerated liquid enters the second high-pressure hydrogenation reactor 211, and the catalyst in the second high-pressure hydrogenation reactor 211 is carried out again Raw treatment；Process filtering of the waste liquid after catalyst by the built-in type filter 212 of the bottom of the second high-pressure hydrogenation reactor 211 Afterwards, discharged from the outlet of the second catalyst regeneration liquid waste or blowback nitrogen inlet pipeline 312.

Fixed bed reactors hydrogenation section 4 includes fixed bed reactors 402, condenser 405, gas-liquid separator 406；

The top of fixed bed reactors 402 is provided with gas-liquid distributor 403, and the bed of fixed bed catalyst 404 is in fixed bed The flat-temperature zone of reactor 402；

The input port of fixed bed reactors 402 connects the of the first high-pressure hydrogenation reactor 201 by Location Detection of Medium Transportation Pipeline Second hydrogenated filtrate pipeline 409 of one hydrogenated filtrate pipeline 410 and the second high-pressure hydrogenation reactor 211, the first hydrogenated filtrate pipe The hydrogenated filtrate pipeline 409 of line 410 and second connects Location Detection of Medium Transportation Pipeline by triple valve 411；

Material-handling pump 401 is provided with Location Detection of Medium Transportation Pipeline；From the first high-pressure hydrogenation reactor 201 or the second high pressure The material of hydrogenation reaction kettle 211 is realized alternately entering fixed bed reactors 402 by the switching of triple valve 411；

The delivery outlet of fixed bed reactors 402 connects the input port of condenser 405, the delivery outlet connection gas of condenser 405 Liquid/gas separator 406；

Gas-liquid separator 406 connects hydrogen pipeloop, and hydrogen gas circulating pump 407 is provided with hydrogen pipeloop；It is fixed The bed connection hydrogen inlet manifold line of reactor 402, hydrogen inlet manifold line and hydrogen pipeloop connect outside constant pressure hydrogen pipe jointly Line 408.

As shown in Fig. 2 serialization catalytic hydrogenation production of the present invention and catalyst recovery process, in closed continuous device Realize that continuous production (can certainly be other hydrogenation products) and the reactor hydrogenation catalyst of hydrogenation product o-chloraniline are former Position regeneration；Comprise the following steps：

Step S1, melting step：First by the pressure-equalizing pipe between the first closed container 101 and the second closed container 102 Line 103 and feedstock transportation pipeline 106 cut off, and solid material o-chloronitrobenzene are added in the first closed container 101, by automatic control Solid-state o-chloronitrobenzene is heated and melted by heating system (not shown)；

Then pressure-equalizing line 103 is connected with feedstock transportation pipeline 106, pressure-equalizing line 103 makes first closed 101 and second closed container of container 102 is isobaric；The o-chloronitrobenzene of melting enters the second closed appearance through feedstock transportation pipeline 106 Device 102；

By the temperature control of the first closed container 101 and the second closed container 102 at 50~150 DEG C；

The o-chloronitrobenzene of melting is delivered to by the first high-pressure hydrogenation reactor 201 or the second by feedstock transportation pump 104 High-pressure hydrogenation reactor 211；Two switchings of high-pressure hydrogenation reactor are realized by triple valve 105；

50~100 DEG C of controlling reaction temperature, 0.5~1.5MPa of pressure, 600~1300r/min of mixing speed, stirring are certainly Suction is stirred；

Material is by the pressure warp in the first high-pressure hydrogenation reactor 201 or the second high-pressure hydrogenation reactor 211 after hydrogenation First built-in type filter 202 or the second built-in type filter 212 enter fixed bed reactors and are hydrogenated with section 4 after filtering；

Hydrogenation catalyst is loaded catalyst, and the composition of hydrogenation catalyst includes active component, auxiliary agent and carrier；Activity Component can be one or more in Pt, Pd, Rh, Ru, Ir, Ni；Auxiliary agent can for Na, K, Mg, Fe, Sn, Ca, Ba, Cr, One or more in Mn, Mo, Zn, Co, rare earth element；Carrier can be activated carbon, modified activated carbon, aluminum oxide, modified oxygen Change one or more in aluminium, silica, molecular sieve, preferably activated carbon；

Hydrogenation catalyst is powder catalyst, such as powdered palladium charcoal, ruthenium charcoal, platinum charcoal, rhodium charcoal, the platinum charcoal containing auxiliary agent, contain (other similar hydrogenation catalysts can also be included certainly one or more in auxiliary agent palladium charcoal, the charcoal of ruthenium containing auxiliary agent, the charcoal of rhodium containing auxiliary agent Agent, the acquisition scope of hydrogenation catalyst should be envisioned that for those skilled in the art, similarly hereinafter)；

Preferably, hydrogenation catalyst is platinum carbon catalyst containing auxiliary agent, and wherein auxiliary agent is one or more in iron, tin, molybdenum, The weight percentage of auxiliary agent is 0.1~5%, and the platinum weight content of platinum charcoal is 1~5%；

Step S3, process catalyst regeneration step：When the first high-pressure hydrogenation reactor 201 or the second high-pressure hydrogenation reactor 211 Hydrogenation catalyst there is deactivation phenomenom, it is necessary to be carried out at regeneration to hydrogenation catalyst when conversion ratio reduction and selectivity are reduced Reason；As catalyst inactivation occurs in reaction in the first high-pressure hydrogenation reactor 201, then stop material and enter, by triple valve 105 Switching makes material be reacted into the second high-pressure hydrogenation reactor 211；After after the hydrogenation in the first high-pressure hydrogenation reactor 201 Material through built-in type filter 202 discharge it is clean after, regenerated liquid is squeezed into by the first high-pressure hydrogenation by regenerated liquid delivery pump 302 anti- Answer in kettle 201, regenerated liquid carries out regeneration treatment to the hydrogenation catalyst in the first high-pressure hydrogenation reactor 201；

600~1200 revs/min of the mixing speed of catalyst regeneration process, 30~90 DEG C of temperature；

Regenerated liquid is selected in one or more in regenerating liquid storage tank 305,306,307,308 as needed；

Built with aqueous alkali, alkali is inorganic base to first regeneration liquid storage tank 305, and mass concentration is 1%~20%, inorganic base Including one or more in NaOH, potassium hydroxide, sodium carbonate, sodium acid carbonate, ammoniacal liquor；

Second regeneration liquid storage tank 306 is built with organic solvent, including alcohols, esters, alkanes, aromatics, alcohols solvent It is one or more in methyl alcohol, ethanol, isopropanol, butanol, esters are one or more in ethyl acetate, butyl acetate, Alkanes be hexamethylene, n-hexane, heptane, octane in one or more, aromatics be benzene,toluene,xylene in one kind or It is various；

3rd regeneration liquid storage tank 307 built with reducing agent aqueous solution, reducing agent be hydrazine hydrate, formaldehyde, formic acid, sodium formate, One or more in potassium borohydride, sodium borohydride, reducing agent aqueous solution weight concentration is 1~10%；

Built with acidic aqueous solution, acid is sulfuric acid, hydrochloric acid, nitric acid, acetic acid, phosphoric acid, perchloric acid to 4th regeneration liquid storage tank 308 In one or more, mass concentration be 0.5~10%；

Step S4, fixed bed reaction step：Material-handling pump 401 will be from the first high-pressure hydrogenation reactor 201 or the second The hydrogenated filtrate of high-pressure hydrogenation reactor 211 squeezes into the top of fixed bed reactors 402, and fixed bed reactors 402 are built with solid Bed catalyst 404；Be input into hydrogen in fixed bed reactors 402 by outside constant pressure hydrogen gas lines 408, and hydrogenated filtrate exists with hydrogen Reacted under the catalytic action of fixed bed catalyst 404, obtained hydrogenation reaction product；Reaction in fixed bed reactors 402 Temperature control is in 40~90 DEG C, 0.5~1MPa of pressure；

Hydrogenation reaction product passes sequentially through condenser 405 and gas-liquid separator 406, by condensation and gas-liquid separation, obtains Hydrogenation product o-chloraniline；

Hydrogen is circulated by hydrogen gas circulating pump 407, and supplements consumed hydrogen by outside constant pressure hydrogen gas lines 408 Gas；

Fixed bed catalyst 404 is loaded catalyst, and the composition of fixed bed catalyst includes active component, auxiliary agent and load Body；Active component can be one or more in Pt, Pd, Rh, Ru, Ir, Ni；Auxiliary agent can for Na, K, Mg, Fe, Sn, Ca, One or more in Ba, Cr, Mn, Mo, Zn, Co, rare earth element；Carrier can for activated carbon, modified activated carbon, aluminum oxide, One or more in modified aluminas, silica, molecular sieve, preferably activated carbon；

Fixed bed catalyst 404 is beaded catalyst, such as one kind or many in graininess platinum charcoal, ruthenium charcoal, palladium charcoal, rhodium charcoal Kind；

Preferably, fixed bed catalyst 404 is that particulate supported type catalyst contains the platinum charcoal of auxiliary agent, auxiliary agent be iron, tin, One or more of molybdenum, the weight content of auxiliary agent is 0.1~5%, and the platinum load capacity of platinum charcoal is weight percentage 0.3~3%.

Description of the invention and application are illustrative, in being not wishing to limit the scope of the invention to above-described embodiment. The deformation and change of embodiments disclosed herein are possible, such as melt zone can be the mixing of material and solvent, hydrogenation Catalyst is changed to add dechlorination inhibitor, catalytic hydrogenation continuous production device in Raney's nickel catalyst, or hydrogenation reaction kettle The replacement implemented for those skilled in the art and can equally be waited with other hydrogenation materials of continuous prodution The various parts of effect are known.It should be appreciated by the person skilled in the art that not departing from spirit of the invention or essence spy In the case of levying, the present invention can in other forms, structure, arrangement, ratio, and with other components, material and part come real It is existing.In the case where scope and spirit of the present invention are not departed from, other deformations can be carried out to embodiments disclosed herein and is changed Become.

Claims

1. a kind of serialization catalytic hydrogenation is produced and catalyst regeneration device, continuous production and reaction for realizing hydrogenation product Kettle hydrogenation catalyst in-situ regeneration；It is characterised in that it includes being connected by pipeline and closed melt zone (1), reactor hydrogenation Section (2), catalyst regenerator section (3), fixed bed reactors are hydrogenated with section (4)；Reactor is hydrogenated with section (2) includes two high pressures of parallel connection Hydrogenation reaction kettle, catalyst regenerator section (3) and wherein one high-pressure hydrogenation reactor composition catalyst original position regenerative system；

Raw material is melted in melt zone (1)；Fused raw material alternately enters two high-pressure hydrogenation reactors of reactor hydrogenation section (2), There is hydrogenation reaction, material after being hydrogenated with hydrogen in the presence of hydrogenation catalyst；Material is by filtering, filtrate after hydrogenation Section (4) is hydrogenated with into fixed bed reactors, is reacted under the catalytic action of fixed bed catalyst (404) with hydrogen, obtained Hydrogenation product；

Hydrogenation reaction and catalyst regeneration process staggeredly are carried out in two high-pressure hydrogenation reactors, when the first high-pressure hydrogenation reactor (201) when carrying out hydrogenation reaction, the catalysagen that the second high-pressure hydrogenation reactor (211) is constituted with catalyst regenerator section (3) Position regenerative system carries out catalyst regeneration process, makes hydrogenation catalyst in second high-pressure hydrogenation reactor (211) interior in-situ regeneration； Hydrogenation reaction in same high-pressure hydrogenation reactor is staggeredly carried out with regeneration treatment.

2. serialization catalytic hydrogenation according to claim 1 is produced and catalyst regeneration device, it is characterised in that described molten Melting section 1 includes the first closed container (101) and the second closed container (102), and the first closed container (101) offers material and enters Mouthful, the first closed container (101) connects the second closed container (102) by feedstock transportation pipeline (106)；

First closed container (101) connects the second closed container (102) by pressure-equalizing line (103), works as pressure-equalizing pipe When line (103) is connected, realize that the first closed container (101) is isobaric with the second closed container (102)；

Second closed container (102) connects the input of feedstock transportation house steward, and the output end of feedstock transportation house steward passes through triple valve (105) input of the first feed inlet lines of connection and the second feed inlet lines, the first feed inlet lines and the second original Expect the first high-pressure hydrogenation reactor (201) and the second high pressure of output end difference coupled reaction kettle hydrogenation section (2) of suction line Hydrogenation reaction kettle (211)；Feedstock transportation pump (104) is provided with feedstock transportation house steward；By the switching of triple valve (105), energy Fused raw material is enough set to interlock into the first high-pressure hydrogenation reactor (201) and the second high-pressure hydrogenation reactor (211).

3. serialization catalytic hydrogenation according to claim 1 is produced and catalyst regeneration device, it is characterised in that described anti- Answering kettle to be hydrogenated with section (2) includes the first high-pressure hydrogenation reactor (201) and the second high-pressure hydrogenation reactor (211) parallel with one another；

The first high-pressure hydrogenation reactor (201) connects the first feed inlet lines, the first hydrogen inlet pipeline (205), the One nitrogen inlet pipeline (203), the first catalyst or deionized water suction line (206), the first dead catalyst outlet line (208), the first catalyst regenerated liquid suction line, the first reactor outlet line；

First hydrogen inlet pipeline (205) and the first nitrogen inlet pipeline (203) are passed through the first high-pressure hydrogenation reactor (201) Top, the first catalyst or deionized water suction line (206) and the first dead catalyst outlet line (208) are passed through the first high pressure The bottom of hydrogenation reaction kettle (201)；

First reactor outlet line connects the first catalyst regeneration liquid waste and exports or blowback nitrogen inlet by triple valve (309) Pipeline (310) and the first hydrogenated filtrate pipeline (410), triple valve (309) can be to the first catalyst regeneration liquid waste outlets or anti- Nitrogen blowing suction line (310) and the first hydrogenated filtrate pipeline (410) are switched over；

First catalyst or deionized water suction line (206) and the first dead catalyst outlet line (208) are by triple valve (207) switch over；First nitrogen inlet pipeline (203) and the first hydrogen inlet pipeline (205) are carried out by triple valve (204) Switching；

First high-pressure hydrogenation reactor (201) is built with the first built-in type filter (202)；First built-in type filter (202) it is high technology ceramics filtration core or precision metallic sintered filter core；

The second high-pressure hydrogenation reactor (211) connects the second feed inlet lines, the second hydrogen inlet pipeline (215), the Two nitrogen suction lines (213), the second catalyst or deionized water suction line (216), the second dead catalyst outlet line (218), the second catalyst regenerated liquid suction line, the second reactor outlet line；

Second hydrogen inlet pipeline (215) and the second nitrogen inlet pipeline (213) are passed through the second high-pressure hydrogenation reactor (211) Top, the second catalyst or deionized water suction line (216) and the second dead catalyst outlet line (218) are passed through the second high pressure The bottom of hydrogenation reaction kettle (211)；

Second reactor outlet line connects the second catalyst regeneration liquid waste and exports or blowback nitrogen inlet by triple valve (311) Pipeline (312) and the second hydrogenated filtrate pipeline (409), triple valve (311) can be to the second catalyst regeneration liquid waste outlets or anti- Nitrogen blowing suction line (312) and the second hydrogenated filtrate pipeline (409) are switched over；

Second catalyst or deionized water suction line (216) and the second dead catalyst outlet line (218) are by triple valve (217) switch over；Second nitrogen inlet pipeline (213) and the second hydrogen inlet pipeline (215) are carried out by triple valve (214) Switching；

Second high-pressure hydrogenation reactor (211) is built with the second built-in type filter (212)；Second built-in type filter (212) it is high technology ceramics filtration core or precision metallic sintered filter core.

4. serialization catalytic hydrogenation according to claim 1 is produced and catalyst regeneration device, it is characterised in that described to urge Agent regenerator section (3) includes at least four regeneration liquid storage tank (305,306,307,308) in parallel, four regeneration liquid storage tanks (305,306,307,308) realize switching by triple valve (303) and four-way valve (304), and by regenerated liquid delivery pump (302) Switching effect with triple valve (301) connects the first high-pressure hydrogenation reactor (201) or the second high-pressure hydrogenation reactor (211).

5. serialization catalytic hydrogenation according to claim 1 is produced and catalyst regeneration device, it is characterised in that described solid Fixed bed reactor is hydrogenated with section (4) includes fixed bed reactors (402), condenser (405), gas-liquid separator (406)；

The top of fixed bed reactors (402) is provided with gas-liquid distributor (403), and fixed bed catalyst (404) bed is in be fixed The flat-temperature zone of bed reactor (402)；

The input port of fixed bed reactors (402) connects the of the first high-pressure hydrogenation reactor (201) by Location Detection of Medium Transportation Pipeline Second hydrogenated filtrate pipeline (409) of one hydrogenated filtrate pipeline (410) and the second high-pressure hydrogenation reactor (211), the first hydrogenation Filtrate line (410) and the second hydrogenated filtrate pipeline (409) connect Location Detection of Medium Transportation Pipeline by triple valve (411)；

Material-handling pump (401) is provided with Location Detection of Medium Transportation Pipeline；From the first high-pressure hydrogenation reactor (201) or the second high pressure The material of hydrogenation reaction kettle (211) is realized alternately entering fixed bed reactors (402) by the switching of triple valve (411)；

The input port of delivery outlet connection condenser (405) of fixed bed reactors (402), the delivery outlet connection of condenser (405) Gas-liquid separator (406)；

Gas-liquid separator (406) connects hydrogen pipeloop, and hydrogen gas circulating pump (407) is provided with hydrogen pipeloop；It is fixed Bed reactor (402) connection hydrogen inlet manifold line, hydrogen inlet manifold line and hydrogen pipeloop connect outside constant pressure hydrogen jointly Pipeline (408).

6. a kind of serialization catalytic hydrogenation production and catalyst recovery process, hydrogenation product is realized in closed continuous device Continuous production and reactor hydrogenation catalyst in-situ regeneration；It is characterised in that it includes following steps：

Step S1, melting step：First by the pressure-equalizing pipe between the first closed container (101) and the second closed container (102) Line (103) and feedstock transportation pipeline (106) are cut off, and solid material is added in the first closed container (101), are heated by automatic control Solid material is heated and melted by system；

Then pressure-equalizing line (103) is connected with feedstock transportation pipeline (106), pressure-equalizing line (103) makes first close Close container (101) isobaric with the second closed container (102)；Fused raw material enters the second closed appearance through feedstock transportation pipeline (106) Device (102)；

Fused raw material is delivered to by the first high-pressure hydrogenation reactor (201) or the second high-pressure hydrogenation by feedstock transportation pump (104) Reactor (211)；Two switchings of high-pressure hydrogenation reactor are realized by triple valve (105)；

Step S2, reactor hydrogenation step：Fresh hydrogenation catalyst passes through the first catalyst or deionized water suction line (206) It is added in the first high-pressure hydrogenation reactor (201)；In the presence of hydrogenation catalyst, the o-chloronitrobenzene of melting with come from There is hydrogenation reaction in the hydrogen of the first hydrogen inlet pipeline (205), in the first high-pressure hydrogenation reactor (201) after being hydrogenated with Material；

Material is by after the built-in type filter (202) of first high-pressure hydrogenation reactor (201) bottom, obtaining hydrogenation filter after hydrogenation Liquid is discharged, by the switching of triple valve (309), by being pumped into fixed bed hydrogenation section (4)；

Or, fresh hydrogenation catalyst is added to the second high-pressure hydrogenation by the second catalyst or deionized water suction line 216 In reactor (211)；In the presence of hydrogenation catalyst, the o-chloronitrobenzene of melting with come from the second hydrogen inlet pipeline (215) there is hydrogenation reaction, material after being hydrogenated with the second high-pressure hydrogenation reactor (211) in hydrogen；

Material is by after the built-in type filter (212) of second high-pressure hydrogenation reactor (211) bottom, obtaining hydrogenation filter after hydrogenation Liquid is discharged, by the switching of triple valve (311), by being pumped into fixed bed hydrogenation section (4)；

Step S3, process catalyst regeneration step：When catalyst inactivation occurs in reaction in the first high-pressure hydrogenation reactor (201), then stop Only material enters, and material is reacted into the second high-pressure hydrogenation reactor (211) by the switching of triple valve (105)；Treat After material is through built-in type filter (202) discharge totally after hydrogenation in first high-pressure hydrogenation reactor (201), by regenerated liquid Delivery pump (302) squeezes into the first high-pressure hydrogenation reactor (201) regenerated liquid, and regenerated liquid is to the first high-pressure hydrogenation reactor (201) hydrogenation catalyst in carries out regeneration treatment；

Waste liquid is by after the filtering of the built-in type filter (202) of first high-pressure hydrogenation reactor (201) bottom after regeneration, from One catalyst regeneration liquid waste is exported or blowback nitrogen inlet pipeline (310) discharge；

Catalyst and deionized water suction line (206) that catalyst after regeneration passes through the first high-pressure hydrogenation reactor (201) Deionized water is squeezed into be washed, cleaning solution by after the filtering of built-in type filter (202), from the first catalyst regeneration liquid waste Outlet or blowback nitrogen inlet pipeline (310) discharge；

The catalyst of built-in type filter (202) surface attachment carries out blowback stripping by blowback nitrogen；By the first catalyst again Raw waste liquid outlet or blowback nitrogen inlet pipeline (310) input blowback nitrogen, the catalyst to filter (202) attachment are carried out instead Blow；

The regeneration treating method and the first high-pressure hydrogenation reactor of the hydrogenation catalyst in the second high-pressure hydrogenation reactor (211) (201) it is identical；

Hydrogenation reaction and catalyst regeneration process staggeredly are carried out in two high-pressure hydrogenation reactors, when the first high-pressure hydrogenation reactor (201) when carrying out hydrogenation reaction, the catalysagen that the second high-pressure hydrogenation reactor (211) is constituted with catalyst regenerator section (3) Position regenerative system carries out catalyst regeneration process, makes hydrogenation catalyst in second high-pressure hydrogenation reactor (211) interior in-situ regeneration； Hydrogenation reaction in same high-pressure hydrogenation reactor is staggeredly carried out with regeneration treatment；

Step S4, fixed bed reaction step：Material-handling pump (401) will be from the first high-pressure hydrogenation reactor (201) or second The hydrogenated filtrate of high-pressure hydrogenation reactor (211) is squeezed into the top of fixed bed reactors (402), fixed bed reactors (402) Equipped with fixed bed catalyst (404)；Be input into hydrogen in fixed bed reactors (402) by outside constant pressure hydrogen gas lines (408), hydrogenation Filtrate is reacted with hydrogen under the catalytic action of fixed bed catalyst (404), obtains hydrogenation reaction product；

Hydrogenation reaction product passes sequentially through condenser (405) and gas-liquid separator (406), by condensation and gas-liquid separation, obtains Hydrogenation product；

Hydrogen is circulated by hydrogen gas circulating pump (407), and supplements consumed hydrogen by outside constant pressure hydrogen gas lines (408) Gas.

7. serialization catalytic hydrogenation according to claim 6 is produced and catalyst recovery process, it is characterised in that the step 50~100 DEG C of the temperature of hydrogenation reaction in rapid S2,0.5~1.5MPa of pressure, 600~1300r/min of mixing speed, stirring are certainly Suction is stirred.

8. serialization catalytic hydrogenation according to claim 6 is produced and catalyst recovery process, it is characterised in that the step Hydrogenation catalyst in rapid S2 is loaded catalyst；The composition of the hydrogenation catalyst includes active component, auxiliary agent and carrier； Active component is one or more in Pt, Pd, Rh, Ru, Ir, Ni；Auxiliary agent be Na, K, Mg, Fe, Sn, Ca, Ba, Cr, Mn, Mo, One or more in Zn, Co, rare earth element；Carrier is activated carbon, modified activated carbon, aluminum oxide, modified aluminas, oxidation One or more in silicon, molecular sieve.

9. serialization catalytic hydrogenation according to claim 6 is produced and catalyst recovery process, it is characterised in that the step Hydrogenation catalyst in rapid S2 be powdered palladium charcoal, ruthenium charcoal, platinum charcoal, rhodium charcoal, the platinum charcoal containing auxiliary agent, the charcoal of palladium containing auxiliary agent, containing auxiliary agent One or more in ruthenium charcoal, the charcoal of rhodium containing auxiliary agent.

10. serialization catalytic hydrogenation according to claim 6 is produced and catalyst recovery process, it is characterised in that described Hydrogenation catalyst in step S2 is platinum carbon catalyst containing auxiliary agent；The auxiliary agent is one or more in iron, tin, molybdenum, auxiliary agent Weight percentage be 0.1~5%, the platinum weight percentage of platinum charcoal is 1~5%.

11. serialization catalytic hydrogenation productions according to claim 6 and catalyst recovery process, it is characterised in that described 600~1200 revs/min of the mixing speed of the catalyst regeneration process in step S3,30~90 DEG C of temperature.

12. serialization catalytic hydrogenation productions according to claim 6 and catalyst recovery process, it is characterised in that described Regenerated liquid in step S3 regenerate liquid storage tank (305,306,307,308) at four in one or more in selected；

Built with aqueous alkali, alkali is inorganic base for first regeneration liquid storage tank (305), and mass concentration is 1%~20%, and inorganic base is One or more in NaOH, potassium hydroxide, sodium carbonate, sodium acid carbonate, ammoniacal liquor；

Built with organic solvent, organic solvent includes that alcohols solvent, esters solvent, alkanes are molten for second regeneration liquid storage tank (306) Agent, aromatic solvents；The alcohols solvent is one or more in methyl alcohol, ethanol, isopropanol, butanol, the esters solvent It it is one or more in ethyl acetate, butyl acetate, the alkane solvents are one in hexamethylene, n-hexane, heptane, octane Plant or various, the aromatic solvents are one or more in benzene,toluene,xylene；

Built with reducing agent aqueous solution, the reducing agent is hydrazine hydrate, formaldehyde, formic acid, formic acid for 3rd regeneration liquid storage tank (307) One or more in sodium, potassium borohydride, sodium borohydride；The reducing agent aqueous solution concentration expressed in percentage by weight is 1~10%；

Built with acidic aqueous solution, the acid is sulfuric acid, hydrochloric acid, nitric acid, acetic acid, phosphoric acid, chlorine high for 4th regeneration liquid storage tank (308) One or more in acid, mass percentage concentration is 0.5~10%.

13. serialization catalytic hydrogenation productions according to claim 6 and catalyst recovery process, it is characterised in that described Reaction temperature in step S4 in fixed bed reactors (402) is controlled in 40~90 DEG C, 0.5~1MPa of pressure.

14. serialization catalytic hydrogenation productions according to claim 6 and catalyst recovery process, it is characterised in that described Fixed bed catalyst (404) is loaded catalyst in step S4, the composition of fixed bed catalyst (404) include active component, Auxiliary agent and carrier；Active component is one or more in Pt, Pd, Rh, Ru, Ir, Ni；Auxiliary agent be Na, K, Mg, Fe, Sn, Ca, One or more in Ba, Cr, Mn, Mo, Zn, Co, rare earth element；Carrier is activated carbon, modified activated carbon, aluminum oxide, modified One or more in aluminum oxide, silica, molecular sieve.

15. serialization catalytic hydrogenation productions according to claim 6 and catalyst recovery process, it is characterised in that described Fixed bed catalyst (404) is one or more in graininess platinum charcoal, ruthenium charcoal, palladium charcoal, rhodium charcoal in step S4；Or, it is described Fixed bed catalyst (404) contains the platinum charcoal of auxiliary agent for particulate supported type catalyst in step S4, and auxiliary agent is iron, tin, molybdenum One or more, the weight percentage of auxiliary agent is 0.1~5%, and the platinum load capacity of platinum charcoal is weight percentage 0.3~3%.

16. serialization catalytic hydrogenation productions according to claim 6 and catalyst recovery process, it is characterised in that described Hydrogenation product is o-chloraniline；The catalyst recovery process is that reactor is hydrogenated with original position of the powder containing auxiliary agent platinum carbon catalyst again Generation method.