CN106866429B

CN106866429B - The production of serialization catalytic hydrogenation and catalyst regeneration device and method

Info

Publication number: CN106866429B
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: 2019-03-15
Anticipated expiration: 2037-04-10
Also published as: CN106866429A

Abstract

The invention discloses a kind of production of serialization catalytic hydrogenation and catalyst regeneration devices, for realizing the continuous production and reaction kettle hydrogenation catalyst in-situ regeneration of hydrogenation product；Including by pipeline connection and closed melt zone, reaction kettle add hydrogen section, catalyst regeneration section, fixed bed reactors to add hydrogen section；Reaction kettle adds hydrogen section to include two high-pressure hydrogenation reaction kettles in parallel, and catalyst regeneration section forms catalyst original position regenerative system with a wherein high-pressure hydrogenation reaction kettle.The present invention can be realized the continuous production of automation control hydrogenation product, and the in-situ regeneration processing of reaction kettle hydrogenation catalyst, so as to extend the use time of catalyst, reduce the loss of catalyst, shorten production procedure, energy consumption is reduced, production efficiency is improved, the hydrogenation product of high quality, high yield can be produced.The invention also discloses a kind of production of serialization catalytic hydrogenation and catalyst recovery process.

Description

The production of serialization catalytic hydrogenation and catalyst regeneration device and method

Technical field

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

Background technique

Currently, 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 that flexible operation, is easy to convert different operation condition and product variety, is suitable for Small mount, multi items, reaction time longer production；The disadvantage is that intermittent discontinuous production, the product of every batch reaction There can be fluctuation due to by operating and being influenced.

Continuous tank reactor, its advantage is that allow continuous production, but needs are compared with multiple reactor series connection or simultaneously Connection, is only applicable in special reaction, and for extending with the trans- time, side reaction increases or selective in complete mixing flow state response Not high hydrogenation reaction.

The common feature of tank reactor is: since catalyst uses in reactor, with increasing for access times, hydrogen Change the phenomenon that catalyst will appear activity decline, leads to selective reduction, side reaction increases, and is unable to meet production needs.For solution The certainly problem makes its activation recovering typically using regeneration treatment is carried out after drawing off catalyst.Chinese patent literature CN102658171B discloses a kind of regeneration method of catalyst for catalytic hydrogenation preparation DSD acid, will draw off catalyst and exists Regenerated carbon supported precious metal catalyst is carried out in tube furnace and reaction kettle.

Fixed bed reactors, its advantage is that operating process is simple, material and hydrogenation technique are easy to adjust, can continuous metaplasia It produces, but has that reaction efficiency is low in itself, the big disadvantage of disposable loaded catalyst cannot solve very well simultaneously for hydrogenation reaction Certainly move heat problem.

O-chloraniline is the important intermediate of pesticide, medicine, fragrance, dyestuff, polyurethane industrial.It is industrial to produce adjacent chlorobenzene The method of amine carries out reduction reaction and obtains o-chloraniline using o-chloronitrobenzene as raw material.Due to iron powder reducing method, sodium sulfide reducing Method, hydrazine hydrate reduction method there is a problem of it is seriously polluted be eliminated, produce the technique that generally uses of o-chloraniline at present and use bone Frame nickel is catalyst, adds desulfurization inhibitor, in methanol or ethanol solution, catalytic hydrogenation o-chloronitrobenzene obtains adjacent chlorobenzene Amine.Due to the presence of reaction process dechlorination, product quality decline is not only resulted in, yield is low, and dechlorination also will cause equipment corrosion, The problems such as catalyst poisoning.If addition solvent can also bring the recycling and environmental pollution of solvent in reaction process, low boiling point is molten Agent brings security risk, 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, 2 ammonium hydroxide of auxiliary agent 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, hydrogen successive reaction in reaction kettle is passed through, after reaction Hydride collected in hydrogenation liquid bath by catalyst filter, catalyst is crossed after filter and carries out reaction kettle weight by blowback It is multiple to use.

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

Chinese patent literature CN100436303 discloses a kind of preparation method of o-chloraniline, is original with o-chloronitrobenzene Material, in the presence of alcoholic solution and catalyst, reacts at 150~250 DEG C, and fully reacting post-processes to obtain o-chloraniline, catalysis Agent is Ru/C, amorphous state NiB, Ni-Fe-B, Ni-Co-B, obtains hydrogen by cracking solvent catalysis.

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 under 70~120 DEG C and 0.5~5.0MPa pressure with hydrogen, reaction Process does not add solvent, carries out adding hydrogen in reaction kettle.

Chinese patent literature CN104098477 discloses a kind of o-nitrochlorobenzene continuous catalytic hydrogenation also original production neighbour chlorobenzene O-nitrochlorobenzene, catalyst, dechlorination inhibitor are put into the good bottom material of hydrogenator cloth, successively use nitrogen by the device and method of amine Gas and hydrogen replace system clean, open inlet valve, by o-nitrochlorobenzene and dechlorination inhibitor mass ratio be 1:0.001~ 0.005:0.001~0.005, is passed through hydrogen, carries out hydrogenation reaction, and 60~100 DEG C of reaction temperature, 0.5~1.5MPa of pressure, hydrogen Change liquid and heat exchanger initially entered by circulating pump, using cross-flow filter, catalyst and part hydride and fresh feed one It rises into injector and goes to recycle, another part hydride continuously produces, and obtains o-chloraniline through subsequent processing.

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 the action of catalyst under the conditions of 25~90 DEG C of temperature Change hydrogenation synthesizing reaction, using fixed bed reactors, using nickel alloy as catalyst, with neutral carrier catalyst carrier.

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

Chinese patent literature CN103360267 discloses a kind of Continuous Liquid Phase catalytic hydrogenating reduction production o-chloraniline side Method, hydrogenation reaction are reacted using multi-floating bodies, and 1# adds with heat exchanger and injector on hydrogen kettle, and part reaction mass is by following Ring pump adds in heat exchanger, injector and 1# to be recycled between hydrogen kettle, and o-nitrochlorobenzene is enable to be fully converted into o-chloraniline, and Suspension separator always is installed behind every hydrogenation reaction kettle, isolates the catalyst in hydride, the catalyst isolated is again It is returned accordingly by circulating pump plus hydrogen kettle is recycled.

Chinese patent literature 201610903803.7 discloses a kind of catalytic hydrogenation continuous production device and production method, It is connected using reaction kettle and fixed bed, centre guarantees continuous production using catalyst separation and return mechanism, but can not be real Existing catalyst on-line regeneration, catalyst separation and returning equipment are more complicated.

In conclusion the production process and device of existing o-chloraniline is produced, there are many defects, the more kettle strings of some need Connection, the catalyst separation equipment of some need complexity, some need add purification apparatus after hydrogen, some need pyroreaction, although Multi-floating bodies allow continuous production, but since reaction kettle 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 cannot can all cause Injury to body and the pollution to environment, still reaction fine catalyst need to draw off regeneration treatment, cause to be catalyzed after inactivating The loss and environmental pollution of agent, while reducing production capacity, simultaneously because o-chloronitrobenzene hydrogenation is there are dechlorination phenomenon, except making Outside at catalyst poisoning, equipment corrosion also will cause, the production cost increases, and equipment safety hidden danger increases.If be added organic molten Agent is reacted it will cause the separation of solvent and purification and loss problem, and production cost and operational hazards are increased.Therefore urgent Need to design the new continuous catalytic hydrogenation production of one kind and its catalyst on-line regeneration technique and device, to overcome existing production The deficiency of technique and device.

Summary of the invention

Technical problem to be solved by the invention is to provide a kind of serialization catalytic hydrogenation production and catalyst regeneration device, The automation control continuous production of hydrogenation product may be implemented in it, to improve production efficiency；Reaction kettle may be implemented simultaneously to add 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 solves Scheme are as follows:

For realizing the continuous production and reaction kettle hydrogenation catalyst in-situ regeneration of hydrogenation product；Including being connected by pipeline And closed melt zone 1, reaction kettle add hydrogen section 2, catalyst regeneration section 3, fixed bed reactors to add hydrogen section 4；Reaction kettle adds hydrogen section 2 Including two high-pressure hydrogenation reaction kettles in parallel, catalyst regeneration section 3 forms catalyst with a wherein high-pressure hydrogenation reaction kettle In-situ regeneration system；

Raw material is melted in melt zone 1；Fused raw material alternately enters two high-pressure hydrogenation reaction kettles that reaction kettle adds hydrogen section 2, Under the action of hydrogenation catalyst with hydrogen occur hydrogenation reaction, obtain plus hydrogen after material；Material is by filtering, filtrate after adding hydrogen Into fixed bed reactors plus hydrogen section 4, is reacted, hydrogenated under the catalytic action of fixed bed catalyst 404 with hydrogen Product；

Hydrogenation reaction and catalyst regeneration process are staggeredly carried out in two high-pressure hydrogenation reaction kettles, when the first high-pressure hydrogenation is anti- When kettle 201 being answered to carry out hydrogenation reaction, the second high-pressure hydrogenation reaction kettle 211 and catalyst composed by catalyst regeneration section 3 are in situ Regenerative system carries out catalyst regeneration process, makes hydrogenation catalyst in-situ regeneration in the second high-pressure hydrogenation reaction kettle 211；It is same Hydrogenation reaction and regeneration treatment in high-pressure hydrogenation reaction kettle staggeredly carry out, to guarantee the continuity of reaction；Whole material is in Air-tight state, material realize automatic conveying.

The melt zone 1 includes the first closed container 101 and the second closed container 102, and the first closed container 101 offers Material inlet, the first closed container 101 connect the second closed container 102 by feedstock transportation pipeline 106；Material is introduced into first Closed container 101 enters the second closed container 102 by feedstock transportation pipeline 106 after the melting of the first closed container 101；The One closed container 101 connects the second closed container 102 by pressure-equalizing line 103, when pressure-equalizing line 103 is connected to, Realize that the first closed container 101 and the second closed container 102 are isobaric；Second closed container 102 connects the defeated of feedstock transportation general pipeline Enter end, the output end of feedstock transportation general pipeline connects the first feed inlet lines and the second feed inlet lines by triple valve 105 Input terminal, the output end of the first feed inlet lines and the second feed inlet lines is separately connected reaction kettle adds hydrogen section 2 One high-pressure hydrogenation reaction kettle 201 and the second high-pressure hydrogenation reaction kettle 211；Feedstock transportation pump 104 is provided on feedstock transportation general pipeline； By the switching of triple valve 105, fused raw material can be made staggeredly to enter the first high-pressure hydrogenation reaction kettle 201 and the second high-pressure hydrogenation Reaction kettle 211.The feedstock transportation pump 104 is metering pump.

The reaction kettle adds hydrogen section 2 to include that the first high-pressure hydrogenation reaction kettle 201 and the second high-pressure hydrogenation parallel with one another are anti- Answer kettle 211；The first high-pressure hydrogenation reaction kettle 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 regeneration liquid suction line, the first reaction kettle 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 reaction kettle 201, the first catalyst or deionized water suction line 206 and first useless Catalyst outlet pipeline 208 is passed through the bottom of the first high-pressure hydrogenation reaction kettle 201；First reaction kettle outlet line passes through triple valve 309 the first catalyst regeneration waste liquid outlets of connection or blowback nitrogen inlet pipeline 310 and the first hydrogenated filtrate pipeline 410, threeway Valve 309 can to the first catalyst regeneration waste liquid outlet or blowback nitrogen inlet pipeline 310 and the first hydrogenated filtrate pipeline 410 into Row switching；First catalyst or deionized water suction line 206 and the first dead catalyst outlet line 208 pass through triple valve 207 It switches 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 provided with the first built-in type filter 202；The connection of second high-pressure hydrogenation reaction kettle 211 second is former Expect 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 regeneration liquid suction line, the second reaction kettle 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 reaction kettle 211, and second urges Agent or deionized water suction line 216 and the second dead catalyst outlet line 218 are passed through the second high-pressure hydrogenation reaction kettle 211 Bottom；Second reaction kettle outlet line connects the second catalyst regeneration waste liquid outlet 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 waste liquid outlet or blowback nitrogen Suction line 312 and the second hydrogenated filtrate pipeline 409 switch 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 reaction kettle 211 is provided 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 Setting formula filter 212 is high technology ceramics filtration core or precision metallic sintered filter core.

The first high-pressure hydrogenation reaction kettle 201 and/or the second high-pressure hydrogenation reaction kettle 211 equipped with temperature monitoring, Pressure detector, automatic control heating device and one or more of cooling device and agitating device.

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

The catalyst regeneration 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 passes through regenerated liquid delivery pump 302 and threeway The switching effect of valve 301 is transported to the first high-pressure hydrogenation reaction kettle 201 or the second high-pressure hydrogenation reaction kettle 211.The regenerated liquid Delivery pump 302 is metering pump.

The fixed bed reactors add hydrogen section 4 to include fixed bed reactors 402, condenser 405, gas-liquid separator 406；Gu The top of fixed bed reactor 402 is equipped with gas-liquid distributor 403, and 404 bed of fixed bed catalyst 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 reaction kettle 201 by Location Detection of Medium Transportation Pipeline Second hydrogenated filtrate pipeline 409 of hydrogenated filtrate pipeline 410 and the second high-pressure hydrogenation reaction kettle 211, the first hydrogenated filtrate pipeline 410 and second hydrogenated filtrate pipeline 409 by triple valve 411 connect Location Detection of Medium Transportation Pipeline；Object is provided on Location Detection of Medium Transportation Pipeline Material conveying pump 401；Material from the first high-pressure hydrogenation reaction kettle 201 or the second high-pressure hydrogenation reaction kettle 211 passes through triple valve 411 switching realization alternately enters fixed bed reactors 402；The delivery outlet of fixed bed reactors 402 connects the defeated of condenser 405 The delivery outlet of entrance, condenser 405 connects gas-liquid separator 406；Gas-liquid separator 406 is connected to hydrogen pipeloop, and hydrogen follows Hydrogen gas circulating pump 407 is provided on endless tube line；Fixed bed reactors 402 are connected to hydrogen inlet manifold line, hydrogen inlet manifold line and hydrogen Gas pipeloop connects external constant pressure hydrogen gas lines 408 jointly.The material-handling pump 401 is metering pump.

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

Step S1, step is melted: 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 to feedstock transportation pipeline 106, pressure-equalizing line 103 makes first closed Container 101 and the second closed container 102 are isobaric；Fused raw material enters the second closed container 102 through feedstock transportation pipeline 106；

Fused raw material is delivered to the first high-pressure hydrogenation reaction kettle 201 or the second high-pressure hydrogenation by feedstock transportation pump 104 Reaction kettle 211；The switching of two high-pressure hydrogenation reaction kettles is realized by triple valve 105；

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

Step S2, reaction kettle hydrogenation step: fresh hydrogenation catalyst passes through the first catalyst or deionized water suction line 206 are added in the first high-pressure hydrogenation reaction kettle 201；Under the action of hydrogenation catalyst, the o-chloronitrobenzene of melting with come from Hydrogenation reaction occurs in the first high-pressure hydrogenation reaction kettle 201 in the hydrogen of the first hydrogen inlet pipeline 205, obtain plus hydrogen after object Material；

Material obtains hydrogenation filter after the built-in type filter 202 of 201 bottom of the first high-pressure hydrogenation reaction kettle after hydrogenation Liquid discharge, by the switching of triple valve 309, delivers into fixed bed hydrogenation section 4 by pump；

Alternatively, 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；Under the action of hydrogenation catalyst, the o-chloronitrobenzene of melting with from the second hydrogen inlet pipeline In the second high-pressure hydrogenation reaction kettle 211 hydrogenation reaction occurs for 215 hydrogen, obtain plus hydrogen after material；

Material obtains hydrogenation filter after the built-in type filter 212 of 211 bottom of the second high-pressure hydrogenation reaction kettle after adding hydrogen Liquid discharge, by the switching of triple valve 311, delivers into fixed bed hydrogenation section 4 by pump；

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

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

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

Preferably, the hydrogenation catalyst in the step S2 is platinum carbon catalyst containing auxiliary agent；The auxiliary agent is iron, tin, molybdenum One of or it is a variety of, 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: there is catalyst inactivation when reacting in the first high-pressure hydrogenation reaction kettle 201, then Stop material entering, so that material is entered the second high-pressure hydrogenation reaction kettle 211 by the switching of triple valve 105 and reacted；To Material passes through regenerated liquid delivery pump after built-in type filter 202 is discharged completely after in one high-pressure hydrogenation reaction kettle 201 plus hydrogen 302 squeeze into regenerated liquid in the first high-pressure hydrogenation reaction kettle 201, and regenerated liquid is in the first high-pressure hydrogenation reaction kettle 201 plus hydrogen Catalyst carries out regeneration treatment；

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

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

The catalyst of 202 surface of built-in type filter attachment carries out blowback removing by blowback nitrogen；Pass through the first catalyst Regeneration liquid waste outlet or blowback nitrogen inlet pipeline 310 input blowback nitrogen, carry out to the catalyst that filter 202 adheres to anti- It blows；

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

Hydrogenation reaction and catalyst regeneration process are staggeredly carried out in two high-pressure hydrogenation reaction kettles, when the first high-pressure hydrogenation is anti- When kettle 201 being answered to carry out hydrogenation reaction, the second high-pressure hydrogenation reaction kettle 211 and catalyst composed by catalyst regeneration section 3 are in situ Regenerative system carries out catalyst regeneration process, makes hydrogenation catalyst in-situ regeneration in the second high-pressure hydrogenation reaction kettle 211；It is same Hydrogenation reaction and regeneration treatment in high-pressure hydrogenation reaction kettle staggeredly carry out；

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

Regenerated liquid in the step S3 in one or more of four regeneration liquid storage tanks 305,306,307,308 into Row selection；First regeneration liquid storage tank 305 is provided with aqueous alkali, and alkali is inorganic base, and mass concentration is 1%~20%, inorganic base It is one or more in sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, ammonium hydroxide；Second regeneration liquid storage tank 306 is provided with Organic solvent, organic solvent include alcohols solvent, esters solvent, alkane solvents, aromatic solvents；The alcohols solvent is first One of alcohol, ethyl alcohol, isopropanol, butanol are a variety of, and the esters solvent is one of ethyl acetate, butyl acetate or more Kind, the alkane solvents are hexamethylene, n-hexane, heptane, one or more in octane, and the aromatic solvents are benzene, first One of benzene, dimethylbenzene are a variety of；Third regeneration liquid storage tank 307 is provided with reducing agent aqueous solution, and the reducing agent is hydration One of hydrazine, formaldehyde, formic acid, sodium formate, potassium borohydride, sodium borohydride are a variety of；The reducing agent aqueous solution weight percent Concentration is 1~10%；4th regeneration liquid storage tank 308 is provided with acidic aqueous solution, the acid be sulfuric acid, hydrochloric acid, nitric acid, acetic acid, One of phosphoric acid, perchloric acid are a variety of, and mass percentage concentration is 0.5~10%.

Step S4, fixed bed reaction step: material-handling pump 401 will come from the first high-pressure hydrogenation reaction kettle 201 or the second The hydrogenated filtrate of high-pressure hydrogenation reaction kettle 211 squeezes into the top of fixed bed reactors 402, and fixed bed reactors 402 are provided with solid Bed catalyst 404；External constant pressure hydrogen gas lines 408 input hydrogen in fixed bed reactors 402, and hydrogenated filtrate and hydrogen exist It is reacted 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 recycled by hydrogen gas circulating pump 407, and supplements consumed hydrogen by external constant pressure hydrogen gas lines 408 Gas.

Reaction temperature control in the step S4 in fixed bed reactors 402 is at 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 of Pt, Pd, Rh, Ru, Ir, Ni or a variety of；Auxiliary agent be Na, K, Mg, Fe, One of Sn, Ca, Ba, Cr, Mn, Mo, Zn, Co, rare earth element are a variety of；Carrier is active carbon, modified activated carbon, oxidation One of aluminium, modified aluminas, silica, molecular sieve are a variety of.

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

Preferably, fixed bed catalyst 404 is that particulate supported type catalyst contains the platinum charcoal of auxiliary agent in the step S4, Auxiliary agent be iron, tin, molybdenum it is one or more, 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 reaction kettle adds the hydrogen powder charcoal of platinum containing auxiliary agent to urge The in situ regeneration method of agent.

What the present invention can achieve has the technical effect that

The present invention utilizes two reaction kettles in parallel, staggeredly plus hydrogen, one in continuously hydrogen adding, in addition one with catalyst again Raw section constitutes catalyst regeneration system, the in-situ regeneration of reaction kettle hydrogenation catalyst is realized, to extend making for hydrogenation catalyst Use the time.

The present invention can be realized the continuous production of automation control hydrogenation product and the original position of reaction kettle hydrogenation catalyst Regeneration treatment reduces the loss of catalyst, shortens production procedure, reduce energy consumption so as to extend the use time of catalyst, Production efficiency is improved, the hydrogenation product of high quality, high yield can be produced.Meanwhile continuous production process of the invention is entirely close It closes, operating environment is excellent, can reduce to the harm of the person and to the pollution of environment.

Detailed description of the invention

It should be understood by those skilled in the art that following explanation is only schematically to illustrate the principle of the present invention, the principle It 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 conceived in this disclosed invention.

It is incorporated in the present specification and forms part of this specification that accompanying drawing shows embodiment of the present invention, and And the principle for explaining the present invention together with the detailed description of general description and following drawings above.

The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments:

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 symbols in figure:

1 is melt zone, and 2 add hydrogen section for reaction kettle,

3 be catalyst regeneration section, and 4 add hydrogen section for fixed bed reactors,

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

103 be pressure-equalizing line, and 104 pump for feedstock transportation,

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

201 be the first high-pressure hydrogenation reaction kettle, and 202 be the first built-in type filter,

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

205 be the first hydrogen inlet pipeline,

206 be the first catalyst or deionized water suction line,

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

211 be the second high-pressure hydrogenation reaction kettle, and 212 be the second built-in type filter,

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

215 be the second hydrogen inlet pipeline,

216 be the second catalyst or deionized water suction line,

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

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

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

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

307 regenerate liquid storage tank for third, and 308 be the 4th regeneration liquid storage tank,

309 be triple valve,

310 be the first catalyst regeneration waste liquid outlet or blowback nitrogen inlet pipeline,

311 be triple valve,

312 be the second catalyst regeneration waste liquid outlet or blowback nitrogen inlet pipeline,

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

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

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

407 be hydrogen gas circulating pump, and 408 be external constant pressure hydrogen gas lines,

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

411 be triple valve.

Specific embodiment

In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention Attached drawing, the technical solution of the embodiment of the present invention is clearly and completely described.Obviously, described embodiment is this hair Bright a part of the embodiment, instead of all the embodiments.Based on described the embodiment of the present invention, ordinary skill Personnel's every other embodiment obtained under the premise of being not necessarily to creative work, shall fall within the protection scope of the present invention.It removes Non- other definition, the technical term or scientific term used herein are should be in fields 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 sequence, Quantity or importance, and be used only to distinguish different component parts.The similar word such as " comprising " means before there is the word The element or object in face are covered the element for appearing in the word presented hereinafter or object and its are equal, and are not excluded for other elements Or object.

As shown in Figure 1, serialization catalytic hydrogenation of the present invention production and catalyst regeneration device, for realizing with adjacent chlorine nitro The continuous production and reaction kettle hydrogenation catalyst in-situ regeneration of benzene preparing o-chloroaniline by catalytic hydrogenation；Including by pipeline connection and Closed melt zone 1, reaction kettle add hydrogen section 2, catalyst regeneration section 3, fixed bed reactors to add hydrogen section 4；Reaction kettle adds hydrogen section 2 to wrap Two high-pressure hydrogenation reaction kettles in parallel are included, catalyst regeneration section 3 forms catalysagen with a wherein high-pressure hydrogenation reaction kettle Position regenerative system；

Raw material o-chloronitrobenzene is melted in melt zone 1；Fused raw material alternately enters reaction kettle and two high pressures of hydrogen section 2 is added to add Hydrogen reaction kettle, under the action of hydrogenation catalyst with hydrogen occur hydrogenation reaction, obtain plus hydrogen after material；Material after hydrogen is added to pass through Filtering, filtrate enter fixed bed reactors and add hydrogen section 4, 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, enters second by feedstock transportation pipeline 106 after the melting of the first closed container 101 Closed container 102；

The top of 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 to, 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.

Reaction kettle adds hydrogen section 2 to include the first high-pressure hydrogenation reaction kettle 201 and the second high-pressure hydrogenation reaction kettle parallel with one another 211；

The input terminal of the bottom connection feedstock transportation general pipeline of second closed container 102, the output end of feedstock transportation general pipeline are logical Cross triple valve 105 connect the first feed inlet lines and the second feed inlet lines input terminal, the first feed inlet lines and The output end of second feed inlet lines is separately connected reaction kettle and adds the first high-pressure hydrogenation reaction kettle 201 and second of hydrogen section 2 high Press hydrogenation reaction kettle 211；Feedstock transportation pump 104, the preferably metering pump of feedstock transportation pump 104 are provided on feedstock transportation general pipeline； By the switching of triple valve 105, fused raw material can be made staggeredly to enter the first high-pressure hydrogenation reaction kettle 201 and the second high-pressure hydrogenation Reaction kettle 211；

First high-pressure hydrogenation reaction kettle 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 first catalyst regeneration waste liquid outlet 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 reaction kettle 201 It is anti-that portion, the first catalyst or deionized water suction line 206 and the first dead catalyst outlet line 208 are passed through the first high-pressure hydrogenation Answer the bottom of kettle 201；

First reaction kettle outlet line connects the first catalyst regeneration waste liquid outlet by triple valve 309 or blowback nitrogen enters Mouth pipeline 310 and the first hydrogenated filtrate pipeline 410, triple valve 309 can be to the first catalyst regeneration waste liquid outlet or blowback nitrogen Gas suction line 310 and the first hydrogenated filtrate pipeline 410 switch over；

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

The bottom of first high-pressure hydrogenation reaction kettle 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 obtains hydrogenation filter after the built-in type filter 202 of 201 bottom of the first high-pressure hydrogenation reaction kettle after hydrogenation Liquid discharge, by the switching of triple valve 309, delivers into fixed bed hydrogenation section 4 by pump；It is high that catalyst regeneration liquid is passed through first The top for pressing hydrogenation reaction kettle 201, waste liquid passes through the built-in type filter of 201 bottom of the first high-pressure hydrogenation reaction kettle after regeneration After 202 filtering, it is discharged from the first catalyst regeneration waste liquid outlet or blowback nitrogen inlet pipeline 310；

The catalyst of 202 surface of built-in type filter attachment carries out blowback removing by blowback nitrogen；Pass through the first catalyst Regeneration liquid waste outlet or blowback nitrogen inlet pipeline 310 input blowback nitrogen, can carry out to the catalyst that filter 202 adheres to Blowback；

Second high-pressure hydrogenation reaction kettle 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 second catalyst regeneration waste liquid outlet 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 reaction kettle 211 It is anti-that portion, the second catalyst or deionized water suction line 216 and the second dead catalyst outlet line 218 are passed through the second high-pressure hydrogenation Answer the bottom of kettle 211；

Second reaction kettle outlet line connects the second catalyst regeneration waste liquid outlet by triple valve 311 or blowback nitrogen enters Mouth pipeline 312 and the second hydrogenated filtrate pipeline 409, triple valve 311 can be to the second catalyst regeneration waste liquid outlet or blowback nitrogen Gas suction line 312 and the second hydrogenated filtrate pipeline 409 switch over；

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

Second high-pressure hydrogenation reaction kettle 211 is provided with the second built-in type filter 212, and the second built-in type filter 212 can 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 entrances are equipped with valve；The pipeline of one-way flow is equipped with check valve；Into the raw material and again of reaction kettle Raw liquid is realized by metering pump to be controlled；

First high-pressure hydrogenation reaction kettle 201 and the second high-pressure hydrogenation reaction kettle 211 may be equipped with temperature monitoring, pressure Detector, automatic control heating device and one or more of cooling device and agitating device；

First high-pressure hydrogenation reaction kettle 201 and the second high-pressure hydrogenation reaction kettle 211 use magnetic agitation or mechanical stirring, stir Mixing mode is self-priming stirring.

Material obtains hydrogenation filter after the built-in type filter 212 of 211 bottom of the second high-pressure hydrogenation reaction kettle after adding hydrogen Liquid discharge, by the switching of triple valve 311, delivers into fixed bed hydrogenation section 4 by pump；It is high that catalyst regeneration liquid is passed through second The top for pressing hydrogenation reaction kettle 211, waste liquid passes through the built-in type filter of 211 bottom of the second high-pressure hydrogenation reaction kettle after regeneration After 212 filtering, it is discharged from the second catalyst regeneration waste liquid outlet or blowback nitrogen inlet pipeline 312；

The catalyst of 212 surface of built-in type filter attachment carries out blowback removing by blowback nitrogen；Pass through the second catalyst Regeneration liquid waste outlet or blowback nitrogen inlet pipeline 312 input blowback nitrogen, can carry out to the catalyst that filter 212 adheres to Blowback.

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

When one of two high-pressure hydrogenation reaction kettles, such as the second high-pressure hydrogenation reaction kettle 211 is used as catalyst treatment When kettle, regenerated liquid enters the second high-pressure hydrogenation reaction kettle 211, carries out again to the catalyst in the second high-pressure hydrogenation reaction kettle 211 Raw processing；Waste liquid after handling catalyst passes through the filtering of the built-in type filter 212 of 211 bottom of the second high-pressure hydrogenation reaction kettle Afterwards, it is discharged from the second catalyst regeneration waste liquid outlet or blowback nitrogen inlet pipeline 312.

Fixed bed reactors add hydrogen section 4 to include fixed bed reactors 402, condenser 405, gas-liquid separator 406；

The top of fixed bed reactors 402 is equipped with gas-liquid distributor 403, and 404 bed of fixed bed catalyst 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 reaction kettle 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 reaction kettle 211, the first hydrogenated filtrate pipe Line 410 and the second hydrogenated filtrate pipeline 409 pass through the connection Location Detection of Medium Transportation Pipeline of triple valve 411；

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

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

Gas-liquid separator 406 is connected to hydrogen pipeloop, is provided with hydrogen gas circulating pump 407 on hydrogen pipeloop；It is fixed Bed reactor 402 is connected to hydrogen inlet manifold line, and hydrogen inlet manifold line and hydrogen pipeloop connect external 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 reaction kettle hydrogenation catalyst of hydrogenation product o-chloraniline are former Position regeneration；The following steps are included:

Step S1, step is melted: 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 o-chloronitrobenzene is added in the first closed container 101, passes through automatic control Heating system (not shown) is by solid-state o-chloronitrobenzene heating melting；

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

The temperature of first closed container 101 and the second closed container 102 is controlled at 50~150 DEG C；

The o-chloronitrobenzene of melting is delivered to the first high-pressure hydrogenation reaction kettle 201 or the second by feedstock transportation pump 104 High-pressure hydrogenation reaction kettle 211；The switching of two high-pressure hydrogenation reaction kettles is realized by triple valve 105；

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

Material is by the pressure warp in the first high-pressure hydrogenation reaction kettle 201 or the second high-pressure hydrogenation reaction kettle 211 after adding hydrogen Enter fixed bed reactors after first built-in type filter 202 or the filtering of the second built-in type filter 212 and adds hydrogen section 4；

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

Hydrogenation catalyst is powder catalyst, and such as powdered palladium charcoal, platinum charcoal, rhodium charcoal, the platinum charcoal containing auxiliary agent, contains ruthenium charcoal One of auxiliary agent palladium charcoal, the charcoal of ruthenium containing auxiliary agent, the charcoal of rhodium containing auxiliary agent or it is a variety of (certainly can also include other similar hydrogenation catalyst Agent, what the acquisition range of hydrogenation catalyst should be envisioned that for those skilled in the art, similarly hereinafter)；

Preferably, hydrogenation catalyst be platinum carbon catalyst containing auxiliary agent, wherein auxiliary agent be one of iron, tin, molybdenum or a variety of, 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 reaction kettle 201 or the second high-pressure hydrogenation reaction kettle 211 Hydrogenation catalyst there is deactivation phenomenom, when conversion ratio reduces and selectivity reduces, need to carry out at regeneration hydrogenation catalyst Reason；If catalyst inactivation occurs in reaction in the first high-pressure hydrogenation reaction kettle 201, then stops material entrance, pass through triple valve 105 Switching reacts material into the second high-pressure hydrogenation reaction kettle 211；After in the first high-pressure hydrogenation reaction kettle 201 plus hydrogen Material through built-in type filter 202 be discharged it is clean after, it is anti-that regenerated liquid is squeezed by the first high-pressure hydrogenation by regenerated liquid delivery pump 302 It answers in kettle 201, regenerated liquid carries out regeneration treatment to the hydrogenation catalyst in the first high-pressure hydrogenation reaction kettle 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 of regeneration liquid storage tank 305,306,307,308 as needed；

First regeneration liquid storage tank 305 is provided with aqueous alkali, and alkali is inorganic base, and mass concentration is 1%~20%, inorganic base Including one or more in sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, ammonium hydroxide；

Second regeneration liquid storage tank 306 is provided with organic solvent, including alcohols, esters, alkanes, aromatics, alcohols solvent For one of methanol, ethyl alcohol, isopropanol, butanol or a variety of, esters are one of ethyl acetate, butyl acetate or a variety of, Alkanes are hexamethylene, n-hexane, heptane, one or more in octane, aromatics be one of benzene,toluene,xylene or It is a variety of；

Third regeneration liquid storage tank 307 is provided with reducing agent aqueous solution, reducing agent be hydrazine hydrate, formaldehyde, formic acid, sodium formate, One of potassium borohydride, sodium borohydride are a variety of, and reducing agent aqueous solution weight concentration is 1~10%；

4th regeneration liquid storage tank 308 is provided with acidic aqueous solution, and acid is sulfuric acid, hydrochloric acid, nitric acid, acetic acid, phosphoric acid, perchloric acid One of or it is a variety of, mass concentration be 0.5~10%；

Step S4, fixed bed reaction step: material-handling pump 401 will come from the first high-pressure hydrogenation reaction kettle 201 or the second The hydrogenated filtrate of high-pressure hydrogenation reaction kettle 211 squeezes into the top of fixed bed reactors 402, and fixed bed reactors 402 are provided with solid Bed catalyst 404；External constant pressure hydrogen gas lines 408 input hydrogen in fixed bed reactors 402, and hydrogenated filtrate and hydrogen exist It is reacted under the catalytic action of fixed bed catalyst 404, obtains hydrogenation reaction product；Reaction in fixed bed reactors 402 Temperature control is at 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 recycled by hydrogen gas circulating pump 407, and supplements consumed hydrogen by external 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 of Pt, Pd, Rh, Ru, Ir, Ni or a variety of；Auxiliary agent can for Na, K, Mg, Fe, Sn, Ca, One of Ba, Cr, Mn, Mo, Zn, Co, rare earth element are a variety of；Carrier can for active carbon, modified activated carbon, aluminium oxide, One of modified aluminas, silica, molecular sieve are a variety of, preferably active carbon；

Fixed bed catalyst 404 is beaded catalyst, such as one of graininess platinum charcoal, ruthenium charcoal, palladium charcoal, rhodium charcoal or more Kind；

Preferably, fixed bed catalyst 404 is that particulate supported type catalyst contains the platinum charcoal of auxiliary agent, auxiliary agent be iron, tin, Molybdenum it is one or more, 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 be it is illustrative, it is not intended to limit the scope of the present invention to the above embodiment. The deformation and change of embodiments disclosed herein are possible, for example melt zone can be the mixing of material and solvent, add hydrogen Catalyst is changed to that dechlorination inhibitor, catalytic hydrogenation continuous production device are added in Raney's nickel catalyst or hydrogenation reaction kettle It the replacement implemented for those skilled in the art and can equally be waited with the other hydrogenation materials of continuous production The various parts of effect are well known.It should be appreciated by the person skilled in the art that special not departing from spirit or essence of the invention In the case where sign, the present invention can in other forms, structure, arrangement, ratio, and with other components, material and component come real It is existing.Without departing from the scope and spirit of the present invention, other deformations can be carried out to embodiments disclosed herein and are changed Become.

Claims

1. a kind of serialization catalytic hydrogenation production and catalyst regeneration device, for realizing the continuous production and reaction of o-chloraniline Kettle hydrogenation catalyst in-situ regeneration, which is characterized in that including by pipeline connection and closed melt zone (1), reaction kettle add hydrogen Section (2), catalyst regeneration section (3), fixed bed reactors add hydrogen section (4)；Reaction kettle adds hydrogen section (2) to include two high pressures in parallel Hydrogenation reaction kettle, catalyst regeneration section (3) form catalyst original position regenerative system with a wherein high-pressure hydrogenation reaction kettle；

Raw material is melted in melt zone (1)；Fused raw material alternately enters two high-pressure hydrogenation reaction kettles that reaction kettle adds hydrogen section (2), Under the action of hydrogenation catalyst with hydrogen occur hydrogenation reaction, obtain plus hydrogen after material；Material is by filtering, filtrate after adding hydrogen Into fixed bed reactors plus hydrogen section (4), is reacted, obtained under the catalytic action of fixed bed catalyst (404) with hydrogen Hydrogenation product；

Hydrogenation reaction and catalyst regeneration process are staggeredly carried out in two high-pressure hydrogenation reaction kettles, when the first high-pressure hydrogenation reaction kettle (201) when carrying out hydrogenation reaction, catalysagen composed by the second high-pressure hydrogenation reaction kettle (211) and catalyst regeneration section (3) Position regenerative system carries out catalyst regeneration process, makes hydrogenation catalyst in second high-pressure hydrogenation reaction kettle (211) interior in-situ regeneration； Hydrogenation reaction and regeneration treatment in same high-pressure hydrogenation reaction kettle staggeredly carry out；

The catalyst regeneration section (3) includes at least four regeneration liquid storage tank (305,306,307,308) in parallel, four regeneration Liquid storage tank (305,306,307,308) realizes switching by triple valve (303) and four-way valve (304), and is conveyed by regenerated liquid Pump (302) is connected to the first high-pressure hydrogenation reaction kettle (201) or the second high-pressure hydrogenation reaction kettle with the switching of triple valve (301) effect (211), the first regeneration liquid storage tank (305) is provided with aqueous alkali, and the second regeneration liquid storage tank (306) is provided with organic solvent, the Three regeneration liquid storage tank (307) are provided with reducing agent aqueous solution, and the 4th regeneration liquid storage tank (308) is provided with acidic aqueous solution.

2. serialization catalytic hydrogenation production according to claim 1 and catalyst regeneration device, which is characterized 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) passes through feedstock transportation pipeline (106) connection the second closed container (102)；

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

Second closed container (102) connects the input terminal of feedstock transportation general pipeline, and the output end of feedstock transportation general pipeline passes through triple valve (105) input terminal of the first feed inlet lines and the second feed inlet lines, the first feed inlet lines and the second original are connected The output end of material suction line is separately connected the first high-pressure hydrogenation reaction kettle (201) and the second high pressure that reaction kettle adds hydrogen section (2) Hydrogenation reaction kettle (211)；Feedstock transportation pump (104) is provided on feedstock transportation general pipeline；Pass through the switching of triple valve (105), energy Fused raw material is enough set staggeredly to enter the first high-pressure hydrogenation reaction kettle (201) and the second high-pressure hydrogenation reaction kettle (211).

3. serialization catalytic hydrogenation production according to claim 1 and catalyst regeneration device, which is characterized in that described anti- Answer kettle that hydrogen section (2) is added to include the first high-pressure hydrogenation reaction kettle (201) and the second high-pressure hydrogenation reaction kettle (211) parallel with one another；

The first high-pressure hydrogenation reaction kettle (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 regeneration liquid suction line, the first reaction kettle outlet line；

First hydrogen inlet pipeline (205) and the first nitrogen inlet pipeline (203) are passed through the first high-pressure hydrogenation reaction kettle (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 reaction kettle outlet line connects the first catalyst regeneration waste liquid outlet 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 waste liquid outlets or anti- Nitrogen blowing suction line (310) and the first hydrogenated filtrate pipeline (410) switch over；

First catalyst or deionized water suction line (206) and the first dead catalyst outlet line (208) pass through triple valve (207) it switches 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 reaction kettle (201) is provided with the first built-in type filter (202)；First built-in type filter It (202) is high technology ceramics filtration core or precision metallic sintered filter core；

The second high-pressure hydrogenation reaction kettle (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 regeneration liquid suction line, the second reaction kettle outlet line；

Second hydrogen inlet pipeline (215) and the second nitrogen inlet pipeline (213) are passed through the second high-pressure hydrogenation reaction kettle (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 reaction kettle outlet line connects the second catalyst regeneration waste liquid outlet 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 waste liquid outlets or anti- Nitrogen blowing suction line (312) and the second hydrogenated filtrate pipeline (409) switch over；

Second catalyst or deionized water suction line (216) and the second dead catalyst outlet line (218) pass through triple valve (217) it switches 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 reaction kettle (211) is provided with the second built-in type filter (212)；Second built-in type filter It (212) is high technology ceramics filtration core or precision metallic sintered filter core.

4. serialization catalytic hydrogenation production according to claim 1 and catalyst regeneration device, which is characterized in that described solid Fixed bed reactor adds hydrogen section (4) to include fixed bed reactors (402), condenser (405), gas-liquid separator (406)；

The top of fixed bed reactors (402) is equipped with gas-liquid distributor (403), and fixed bed catalyst (404) bed, which is in, to 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 reaction kettle (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 reaction kettle (211), the first hydrogenation Filtrate line (410) and the second hydrogenated filtrate pipeline (409) pass through triple valve (411) connection Location Detection of Medium Transportation Pipeline；

Material-handling pump (401) are provided on Location Detection of Medium Transportation Pipeline；From the first high-pressure hydrogenation reaction kettle (201) or the second high pressure The material of hydrogenation reaction kettle (211) alternately enters fixed bed reactors (402) by the switching realization 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) is connected to hydrogen pipeloop, is provided with hydrogen gas circulating pump (407) on hydrogen pipeloop；It is fixed Bed reactor (402) is connected to hydrogen inlet manifold line, and hydrogen inlet manifold line and hydrogen pipeloop connect external constant pressure hydrogen jointly Pipeline (408).

5. a kind of serialization catalytic hydrogenation production and catalyst recovery process, realize o-chloraniline in closed continuous device Continuous production and reaction kettle hydrogenation catalyst in-situ regeneration；Characterized by comprising the following steps:

Step S1, step is melted: 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) cutting, solid material is added in the first closed container (101), is heated by automatic control System is by solid material heating melting；

Then pressure-equalizing line (103) is connected to feedstock transportation pipeline (106), pressure-equalizing line (103) makes first close It is isobaric to close container (101) and 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 the first high-pressure hydrogenation reaction kettle (201) or the second high-pressure hydrogenation by feedstock transportation pump (104) Reaction kettle (211)；The switching of two high-pressure hydrogenation reaction kettles is realized by triple valve (105)；

Step S2, reaction kettle 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 reaction kettle (201)；Under the action of hydrogenation catalyst, the o-chloronitrobenzene of melting with from Hydrogenation reaction occurs in the first high-pressure hydrogenation reaction kettle (201) for the hydrogen of the first hydrogen inlet pipeline (205), obtains after adding hydrogen Material；

Material obtains hydrogenation filter after the built-in type filter (202) of first high-pressure hydrogenation reaction kettle (201) bottom after hydrogenation Liquid discharge, by the switching of triple valve (309), delivers into fixed bed hydrogenation section (4) by pump；

Alternatively, fresh hydrogenation catalyst is added to the second high-pressure hydrogenation by the second catalyst or deionized water suction line 216 In reaction kettle (211)；Under the action of hydrogenation catalyst, the o-chloronitrobenzene of melting with from the second hydrogen inlet pipeline (215) hydrogenation reaction occurs in the second high-pressure hydrogenation reaction kettle (211) for hydrogen, obtain plus hydrogen after material；

Material obtains hydrogenation filter after the built-in type filter (212) of second high-pressure hydrogenation reaction kettle (211) bottom after adding hydrogen Liquid discharge, by the switching of triple valve (311), delivers into fixed bed hydrogenation section (4) by pump；

Step S3, process catalyst regeneration step: there is catalyst inactivation when reacting in the first high-pressure hydrogenation reaction kettle (201), then stop Only material enters, and so that material is entered the second high-pressure hydrogenation reaction kettle (211) by the switching of triple valve (105) and is reacted；To Material passes through regenerated liquid after built-in type filter (202) discharge is clean after in first high-pressure hydrogenation reaction kettle (201) plus hydrogen Delivery pump (302) squeezes into regenerated liquid in the first high-pressure hydrogenation reaction kettle (201), and regenerated liquid is to the first high-pressure hydrogenation reaction kettle (201) hydrogenation catalyst in carries out regeneration treatment；

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

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

The catalyst of built-in type filter (202) surface attachment carries out blowback removing by blowback nitrogen；Again by the first catalyst Raw waste liquid outlet or blowback nitrogen inlet pipeline (310) input blowback nitrogen, carry out to the catalyst of filter (202) attachment anti- It blows；

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

Step S4, fixed bed reaction step: material-handling pump (401) will come from the first high-pressure hydrogenation reaction kettle (201) or second The hydrogenated filtrate of high-pressure hydrogenation reaction kettle (211) squeezes into the top of fixed bed reactors (402), and fixed bed reactors (402) are interior Equipped with fixed bed catalyst (404)；External constant pressure hydrogen gas lines (408) hydrogenate in hydrogen input fixed bed reactors (402) Filtrate is reacted under the catalytic action of fixed bed catalyst (404) with hydrogen, 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 recycled by hydrogen gas circulating pump (407), and supplements consumed hydrogen by external constant pressure hydrogen gas lines (408) Gas.

6. serialization catalytic hydrogenation production according to claim 5 and catalyst recovery process, which is characterized in that the step 50~100 DEG C of temperature, 0.5~1.5MPa of pressure, 600~1300r/min of mixing speed of hydrogenation reaction in rapid S2, are stirred as certainly Suction stirring.

7. serialization catalytic hydrogenation production according to claim 5 and catalyst recovery process, which is characterized 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 of Pt, Pd, Rh, Ru, Ir, Ni or a variety of；Auxiliary agent be Na, K, Mg, Fe, Sn, Ca, Ba, Cr, Mn, Mo, One of Zn, Co, rare earth element are a variety of；Carrier is active carbon, modified activated carbon, aluminium oxide, modified aluminas, oxidation One of silicon, molecular sieve are a variety of.

8. serialization catalytic hydrogenation production according to claim 5 and catalyst recovery process, which is characterized in that the step Hydrogenation catalyst in rapid S2 is powdered palladium charcoal, ruthenium charcoal, platinum charcoal, rhodium charcoal, the platinum charcoal containing auxiliary agent, the charcoal of palladium containing auxiliary agent, contains auxiliary agent One of ruthenium charcoal, the charcoal of rhodium containing auxiliary agent are a variety of.

9. serialization catalytic hydrogenation production according to claim 5 and catalyst recovery process, which is characterized in that the step Hydrogenation catalyst in rapid S2 is platinum carbon catalyst containing auxiliary agent；The auxiliary agent be one of iron, tin, molybdenum or a variety of, auxiliary agent Weight percentage is 0.1~5%, and the platinum weight percentage of platinum charcoal is 1~5%.

10. serialization catalytic hydrogenation production according to claim 5 and catalyst recovery process, which is characterized in that described 600~1200 revs/min of the mixing speed of catalyst regeneration process in step S3,30~90 DEG C of temperature.

11. serialization catalytic hydrogenation production according to claim 5 and catalyst recovery process, which is characterized in that described Regenerated liquid in step S3 is selected in one or more of four regeneration liquid storage tanks (305,306,307,308)；

First regeneration liquid storage tank (305) is provided with aqueous alkali, and alkali is inorganic base, and mass concentration is 1%~20%, and inorganic base is It is sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, one or more in ammonium hydroxide；

Second regeneration liquid storage tank (306) is provided with organic solvent, and organic solvent includes that alcohols solvent, esters solvent, alkanes are molten Agent, aromatic solvents；The alcohols solvent is one of methanol, ethyl alcohol, isopropanol, butanol or a variety of, the esters solvent For one of ethyl acetate, butyl acetate or a variety of, the alkane solvents be hexamethylene, n-hexane, heptane, one in octane Kind is a variety of, and the aromatic solvents are one of benzene,toluene,xylene or a variety of；

Third regeneration liquid storage tank (307) is provided with reducing agent aqueous solution, and the reducing agent is hydrazine hydrate, formaldehyde, formic acid, formic acid One of sodium, potassium borohydride, sodium borohydride are a variety of；The reducing agent aqueous solution concentration expressed in percentage by weight is 1~10%；

4th regeneration liquid storage tank (308) is provided with acidic aqueous solution, and the acid is sulfuric acid, hydrochloric acid, nitric acid, acetic acid, phosphoric acid, high chlorine One of acid is a variety of, and mass percentage concentration is 0.5~10%.

12. serialization catalytic hydrogenation production according to claim 5 and catalyst recovery process, which is characterized in that described Reaction temperature control in step S4 in fixed bed reactors (402) is at 40~90 DEG C, 0.5~1MPa of pressure.

13. serialization catalytic hydrogenation production according to claim 5 and catalyst recovery process, which is characterized in that described In step S4 fixed bed catalyst (404) be loaded catalyst, the composition of fixed bed catalyst (404) include active component, Auxiliary agent and carrier；Active component is one of Pt, Pd, Rh, Ru, Ir, Ni or a variety of；Auxiliary agent be Na, K, Mg, Fe, Sn, Ca, One of Ba, Cr, Mn, Mo, Zn, Co, rare earth element are a variety of；Carrier is active carbon, modified activated carbon, aluminium oxide, modification One of aluminium oxide, silica, molecular sieve are a variety of.

14. serialization catalytic hydrogenation production according to claim 5 and catalyst recovery process, which is characterized in that described Fixed bed catalyst (404) is one of graininess platinum charcoal, ruthenium charcoal, palladium charcoal, rhodium charcoal or a variety of in step S4；Alternatively, described Fixed bed catalyst (404) is the platinum charcoal that particulate supported type catalyst contains auxiliary agent 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%.

15. serialization catalytic hydrogenation production according to claim 5 and catalyst recovery process, which is characterized in that described Catalyst recovery process is the in situ regeneration method that reaction kettle adds hydrogen powder platinum carbon catalyst containing auxiliary agent.