CN106984294B - A kind of oxidative carbonylation synthesis technique, its liquid waste processing catalyst and preparation method thereof - Google Patents
A kind of oxidative carbonylation synthesis technique, its liquid waste processing catalyst and preparation method thereof Download PDFInfo
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- CN106984294B CN106984294B CN201611100241.9A CN201611100241A CN106984294B CN 106984294 B CN106984294 B CN 106984294B CN 201611100241 A CN201611100241 A CN 201611100241A CN 106984294 B CN106984294 B CN 106984294B
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Abstract
The invention discloses a kind of oxidative carbonylation synthesis technique, its liquid waste processing catalyst and preparation method thereof.The synthesis technique, use nitric oxide to generate nitrous acid ester for nitric acid caused by the reaction of reducing agent reduction-oxidation carbonylation and put into oxidative carbonylation synthesis again, form the lossless circulation of nitrogen.The liquid waste processing catalyst, is carbon attachment material, including matrix and the carbon material layer for being covered in stromal surface；The carbon material layer is loose structure, including the carbon material of mass fraction 85%~95% and 5%~15% binding agent；The matrix is tower structured packing or random packing.The catalyst can greatly improve nitric acid transformation efficiency.
Description
Technical field
The invention belongs to chemical field, more particularly, to a kind of oxidative carbonylation synthesis technique, its liquid waste processing
Catalyst and preparation method thereof.
Background technology
The chemical waste liquid containing dust technology, nitric oxide waste gas can be all produced in oxidative carbonylation esters synthesis technique, with
Exemplified by the commercial synthesis of oxalate and carbonic ester：Following reaction occurs in building-up process：
(1) 2RONO+2CO=ROOCCOOR+2NO
(2) 2RONO+CO=ROOCOR+2NO
Reaction 1,2 is respectively the reaction equations of oxalate and carbonic ester, in reaction is raw into nitric oxide (NO) must turn
Turn to nitrous acid ester ability maintenance reaction to be carried out continuously, there is following reaction during NO is converted into nitrous acid ester：
(3)4ROH+4NO+O2=4RONO+2H2O
Wherein R:Represent alkyl, such as CH3-, C2H5.
(4)4NO+3O2+2H2O=4HNO3
Reaction equation 3 is the regenerative response of nitrous acid ester, and reaction 4 is side reaction in nitrous acid ester regenerative process, raw in reaction 3
Into water be mixed to form dust technology with the nitric acid of by-product and unreacted methanol in reaction 4, its concentration of nitric acid typically 0.5~
Between 10%.It is not intended to react 4 in nitrous acid ester regenerative process, though numerous researchs are intended to improve the selection of nitrous acid ester
Property, but still the generation of reaction 4 can not be avoided completely.
These chemical waste liquids containing dust technology handle the nitre in mixed solution using the methods of rectifying recovery, neutralization at present
Acid, but these methods have shortcomings, when being reclaimed such as rectifying nitric acid in concentration process in addition to a large amount of steam are consumed, can also be with
Other components such as material such as alcohol, ester reacts, and nitric acid can decompose at high temperature simultaneously for generation aldehyde, acid；And in nitric acid and it can disappear
Substantial amounts of alkali is consumed, the nitrate of by-product also needs further to handle.Patent CN03120703.0 description one kind utilizes oxalate by-product
Nitric acid synthesizes the synthetic method of nitrous acid ester, and this method is suitable as the supplement of oxalic acid Lipase absobed Central Asia nitrate, it is impossible to be used in
Dust technology is handled, nitric acid conversion ratio highest only has 80% in embodiment, and the dust technology that also concentration is 1.9% is remaining.Closely
To utilize the dilute nitre of Reduction of methanol using methanol oxidation reduction dust technology generation methyl nitrite, the method in patent CN104945262A
Acid has the characteristics of reaction condition is gentle, nitric acid high conversion rate, but consumes a large amount of methanol as reducing agent using methanol, handles
Dust technology cost is higher；Patent CN104338550A uses the activated carbon of covering molecular screen membrane to pass through load iron, copper etc. for carrier
Auxiliary agent, for the catalyst for the processing of oxalic acid Lipase absobed dust technology, nitric acid conversion ratio is 70%, because addition copper, iron are as auxiliary agent,
Copper, iron are easily dissolved by nitric acid under dust technology environment, so as to influence the stability of catalyst.
, such as dust technology be present in the method that oxidative carbonylation synthesis at present there is no chemical waste liquid of the processing containing dust technology very well
The problem of processing is incomplete, catalyst is unstable and processing cost is high, N element loss needs are continuously replenished, ultimately caused whole
Individual synthesis technique cost is higher and unfriendly to environment.
The content of the invention
For the disadvantages described above or Improvement requirement of prior art, the invention provides a kind of oxidative carbonylation synthesis technique,
Its liquid waste processing catalyst and preparation method thereof, its object is to final by nitric oxide reduction nitric acid caused by synthetic reaction
Nitrous acid ester is generated as oxidative carbonylation synthesis material, the lossless circulation of N element is formed, thus solves existing oxidative carbonylation N
The technical problem of element loss.
To achieve the above object, according to one aspect of the present invention, there is provided a kind of oxidative carbonylation synthesizes liquid waste processing
Catalyst, it is characterised in that be carbon attachment material；The carbon attachment material includes matrix and is covered in the carbon of stromal surface
Material layer；The carbon material layer is loose structure, including the carbon material of mass fraction 85%~98% and 2%~15% is bonded
Agent；The matrix is tower structured packing or random packing.
Preferably, described catalyst, its described carbon material layer also include the auxiliary agent that mass fraction is 0.1%~10%,
It is preferred that B or Pt.
Preferably, described catalyst, its described binding agent are tar or epoxy resin；The matrix is ceramic, stainless
Steel and/or plastic material；The carbon material is.
According to another aspect of the present invention, there is provided a kind of preparation method of described catalyst, comprise the following steps：
A, by carbon material carry out it is scattered form dispersion, gas can be used scattered as air is scattered or liquid dispersion, such as
Carbon material and dispersant, binding agent are uniformly mixed to form carbon material dispersion liquid；
B, the carbon material dispersion obtained in step A is uniformly attached to stromal surface, obtains carbon material-matrix composite
Body；
C, the carbon material obtained in step B-substrate complex is subjected to attached shape processing, obtains the carbon-supported catalysts.
According to another aspect of the present invention, there is provided a kind of oxidative carbonylation synthesis technique, it comprises the following steps：
Oxidative carbonylation synthesizes：Oxidation and carbonylation occurs as raw material using the gas containing nitrous acid ester and carbon monoxide to close
Into the nitric oxide of generation carries out nitrous acid ester regenerative response, obtains the chemical waste liquid of containing alcohol and dust technology and containing an oxidation
The synthetic cyclic gas of nitrogen；
Waste liquid nitric acid treatment：
(1) it is the caused chemical waste liquid containing alcohol and dust technology in oxidative carbonylation synthetic reaction is nitric oxide production with containing
Synthetic cyclic gas, cocurrent or countercurrent pass through catalyst bed, the liquid and gas after being handled；
(2) alcohol in the liquid phase after the processing obtained in recycling step (1), obtains the liquid phase after dealcoholysis；
(3) liquid phase after the dealcoholysis that will be obtained in step (2) is former as the liquid containing nitrous acid ester that oxidative carbonylation synthesizes
Material input；
(4) gas phase after the processing that will be obtained in step (1), the gas of the oxidative carbonylation synthesis containing carbon monoxide is put into
Body raw material.
Preferably, described oxidative carbonylation synthesis technique, its catalyst bed, the catalyst of filling is for activated carbon or as weighed
Profit wants the catalyst described in 1 to 3.
Preferably, described oxidative carbonylation synthesis technique, its described chemical waste liquid, wherein concentration of nitric acid are less than or equal to
10%；The synthetic cyclic gas, wherein nitric oxide production percent by volume is between 1% to 20%；Preferably, the chemical industry gives up
Liquid and synthetic cyclic gas are by preheating.
Preferably, described oxidative carbonylation synthesis technique, when passing through catalyst bed using cocurrent, the chemical industry gives up for it
Liquid and synthetic cyclic gas are by premix.
Preferably, described oxidative carbonylation synthesis technique, when its cocurrent or countercurrent passes through catalyst bed, wherein liquid phase is empty
Speed is in 0.1h-1~3h-1Between, gas phase air speed is in 100h-1~3000h-1Between.
Preferably, described oxidative carbonylation synthesis technique, its described catalyst bed temperature control 30~120 DEG C it
Between, reaction pressure is in 0.1Mpa between 1.50Mpa.
In general, by the contemplated above technical scheme of the present invention compared with prior art, it can obtain down and show
Beneficial effect：
The present invention disposed waste liquid using nitric oxide caused by oxidative carbonylation synthesis technique as reducing agent in nitric acid most
Oxidation and carbonylation is put into nitrous acid ester throughout one's life, forms that N element is lossless recycles, efficiently, low-cost processes nitrous acid ester
By-product nitric acid in during regeneration, it is environment-friendly.Using catalyst provided by the invention, nitric acid treatment efficiency greatly improves.
Brief description of the drawings
Fig. 1 is oxidative carbonylation synthesis technique schematic flow sheet provided by the invention；
Fig. 2 is the waste liquid nitric acid treatment apparatus structure schematic diagram that the embodiment of the present invention 1,2 and 4 uses；
Fig. 3 is the waste liquid nitric acid treatment apparatus structure schematic diagram that the embodiment of the present invention 3 and 5 uses.
In all of the figs, identical reference is used for representing identical element or structure, wherein：1 is mixing column, 2
It is tower reactor circulating pump for feed preheater, 3,4 be packed tower, and 5 be reaction tower.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in each embodiment of invention described below
Conflict can is not formed each other to be mutually combined.
Oxidative carbonylation provided by the invention synthesizes liquid waste processing catalyst, is a kind of carbon-supported catalysts, adheres to for carbon
Material；The carbon attachment material includes matrix and is covered in the carbon material layer of stromal surface.The carbon material layer is loose structure,
Carbon material including mass fraction 85%~98%, 2%~15% binding agent and 0.1%~10% auxiliary agent.The carbon
The preferred carbon dust of material, activated carbon, and/or carbon nanomaterial；The preferred tar of the binding agent or epoxy resin；The auxiliary agent be B,
Or Pt etc..
The matrix can use existing tower structured packing or random packing, preferably ceramic, stainless steel and/or plastics material
Matter.
The carbon-supported catalysts, are prepared as follows：
A, by carbon material carry out it is scattered form dispersion, gas can be used scattered as air is scattered or liquid dispersion, such as
Carbon material and dispersant, binding agent are uniformly mixed to form carbon material dispersion liquid；
B, the carbon material dispersion obtained in step A is uniformly attached to stromal surface, obtains carbon material-matrix composite
Body；
C, the carbon material obtained in step B-substrate complex is subjected to attached shape processing, obtains the carbon-supported catalysts；
The attached shape processing includes drying, roasting, and/or activation process.
Carbon-supported catalysts provided by the invention are exclusively used in oxidative carbonylation synthesis provided by the invention
Oxidative carbonylation synthesis technique provided by the invention, as shown in figure 1, comprising the following steps：
Oxidative carbonylation synthesizes：Oxidative carbonylation is occurred as raw material using the liquid containing nitrous acid ester and the gas containing carbon monoxide
Reaction synthesis, the nitric oxide of generation carry out nitrous acid ester regenerative response, obtain the chemical waste liquid of containing alcohol and dust technology and contain
Nitric oxide production synthetic cyclic gas；Regenerative response is as follows：
4ROH+4NO+O2=4RONO+2H2O (I)
4NO+3O2+2H2O=4HNO3 (II)
Wherein formula (I) is nitrate regenerative response formula, and formula (II) is side reaction, and R represents alkyl, such as CH3-、C2H5Deng.
Waste liquid nitric acid treatment：
(1) it is the caused chemical waste liquid containing alcohol and dust technology in oxidative carbonylation synthetic reaction is nitric oxide production with containing
Synthetic cyclic gas, cocurrent or countercurrent pass through catalyst bed, the liquid and gas after being handled；Following chemical reaction occurs：
2HNO3+ 4NO=6N2O3+H2O (Ⅲ)
2ROH+N2O3=2RONO+H2O (Ⅳ)
The chemical waste liquid, wherein concentration of nitric acid are less than or equal to 10%；The synthetic cyclic gas, wherein nitric oxide production body
Product percentage is between 1% to 20%；Preferably, the chemical waste liquid and synthetic cyclic gas be by preheating, when using and flow through
When crossing catalyst bed, the chemical waste liquid and synthetic cyclic gas are by premix.
When cocurrent or countercurrent passes through catalyst bed, wherein liquid phase air speed is in 0.1h-1~3h-1Between, gas phase air speed is in 100h-1~3000h-1Between, wherein liquid phase air speed preferably 0.5~2h-1, the excellent 100~1000h of gas phase air speed-1；The catalyst bed temperature
Degree control is between 30~120 DEG C, and reaction pressure is in 0.1Mpa between 1.50Mpa.
When concentration of nitric acid is less than or equal to 5%, preferably cocurrent passes through catalyst bed；It is excellent when concentration of nitric acid is more than 5%
Choosing adverse current passes through catalyst bed.
The catalyst bed, the catalyst of filling is activated carbon or carbon-supported catalysts provided by the invention.
(2) alcohol in the liquid phase after the processing obtained in recycling step (1), obtains the liquid phase after dealcoholysis；
(3) liquid phase after the dealcoholysis that will be obtained in step (2) is put into as oxidative carbonylation synthetic reaction raw material；
(4) gas phase after the processing that will be obtained in step (1), the gas of the oxidative carbonylation synthesis containing carbon monoxide is put into
Body raw material.
Oxidative carbonylation synthesis technique provided by the invention, the commercial synthesis process suitable for including oxalate and carbonic ether
Chemical industry synthesis inside, it is just specific again as reducing agent because its commercial synthesis process is generated containing the waste gas for equally changing nitrogen
The dust technology in chemical waste liquid is reduced in the presence of catalyst, obtains nitrogen dioxide, nitrogen dioxide further with nitric oxide and
Alcohol reaction generation nitrate, dust technology caused by synthesis side reaction is re-used, realizes the complete circulation of nitrogen, is solved
The power Cost Problems of dust technology waste liquid and and the not exclusively caused environmental problem of processing.
On the other hand, catalyst provided by the invention combines the process conditions of the present invention, and dust technology catalytic conversion arrives
Greatly improve, for nitric acid conversion ratio more than 90%, preferred scheme reaches 98%.
It is embodiment below：
The oxidative carbonylation synthesis of oxalate of embodiment 1
The activated carbon that the catalyst that the present embodiment uses is modified for B, specific practice by the activated carbon activated in mass ratio
Example B:AC=1:20 ratio adds boric acid aqueous solution incipient impregnation, in 500~600 DEG C of isolation skies after 120 DEG C of drying 2 hours
Gas is calcined 2h, and 3 catalyst that can obtain this example are washed with being embathed containing bodies such as aqueous solution of nitric acid after isolation air cooling.
The technological process that the present embodiment uses, waste liquid nitric acid treatment accompanying drawing 2, using mixing column as reactor, tower epimere
As sizer, filler is catalyst granules, is divided to two sections of fillings；Hypomere is plate column.
The present embodiment flow is shown in Fig. 2：
Oxidative carbonylation synthesizes：
Oxidation and carbonylation synthesis of oxalate is occurred as raw material using the liquid containing nitrous acid ester and the gas containing carbon monoxide,
The nitric oxide of generation carries out nitrous acid ester regenerative response, obtains the chemical waste liquid of containing alcohol and dust technology and containing nitric oxide production
Synthetic cyclic gas；Regenerative response is as follows：
4ROH+4NO+O2=4RONO+2H2O (I)
4NO+3O2+2H2O=4HNO3 (II)
Wherein formula (I) is nitrate regenerative response formula, and formula (II) is side reaction, and R represents CH3Or C2H5。
Waste liquid nitric acid treatment：
(1) caused chemical waste liquid in said process is heated to 80 DEG C of towers from the mixing column 1 through feed preheater
Top adds, and liquid air speed is 1.0h-1；During above-mentioned oxidative carbonylation caused synthetic cyclic gas through valve 4 from the bottom of mixing column 1
Portion enters, gas phase air speed 200h-1, reactor pressure 0.1Mpa；Tower bottoms is heated to 90~100 DEG C through feed preheater 2, from upper
Portion's column plate is sprayed and heated is heated to 85 DEG C into tower reaction gas, reaction gas through tower bottoms, enters catalyst layer from filler bottom, makes
Gas is obtained with liquid in beds counter current contacting；The catalyst bed temperature control is at 80~90 DEG C.
The chemical waste liquid after measured, containing (mass fraction) nitric acid 1% and methanol 55%, water 43%.
After measured, concrete composition (percent by volume) is as follows for the synthetic cyclic gas：Nitric oxide 12%, methyl nitrite
5%th, carbon monoxide 15%, carbon dioxide 10%, methanol 8% and nitrogen 50%.
(2) reacted liquid phase mixes with tower reactor circulation fluid on tower tray, is sent through tower reactor circulating pump 3 and out-of-bounds goes Methanol Recovery
System.
(3) reaction raw materials of the liquid phase after Methanol Recovery is handled as oxalate, oxidative carbonylation system is put into again.
(4) synthetic cyclic gas is after catalyst layer contacts with reaction solution, by about 95% nitrate reductase in reaction solution, after reaction
Gas enters oxalic acid Lipase absobed through tower top valve 3.
In the present embodiment, other conditions are constant, and liquid air speed only is adjusted into 0.1h-1~0.5h-1When, in reaction solution about
90% to 93% nitric acid is reduced.
The oxidative carbonylation synthesis of oxalate of embodiment 2
The carbon-supported catalysts that the present embodiment uses is carbon attachment materials；The carbon attachment material includes matrix and is covered in base
The carbon material layer on matter surface.The carbon material layer is loose structure, including the powdered carbon of mass fraction 90%~95%, 5%~
10% tar.
The matrix is the ceramic packing after the processing 3~5 hours of 100 DEG C of 5% potassium hydroxide.
The carbon-supported catalysts are prepared as follows：
A, the powdered carbon of formula rate, blended tars are heated to 120 DEG C, stir to form carbon material dispersion liquid；
B, the ceramic packing after the processing 3~5 hours of 100 DEG C of 5% potassium hydroxide is submerged into above-mentioned dispersion liquid, impregnated
Taken out after 0.5 hour and drain 2h so that carbon material, which is scattered in, is uniformly attached to ceramic packing surface, obtains carbon material-matrix
Complex；
C, the carbon material-substrate complex is completely cut off into air roasting 4h at 600~750 DEG C, is then warming up to 900 DEG C and leads to
Enter 0.5 hour catalyst for obtaining this example of steam activation.
The technological process that the present embodiment uses, waste liquid nitric acid treatment refers to accompanying drawing 2, using packed tower as reactor, tower
Epimere is sizer, and filler is covers carbon ceramics filler catalyst, point four sections of fillings；Tower body lowermost dress stainless steel metal ripple is filled out
Material.
The present embodiment flow is shown in Fig. 2：
Oxidative carbonylation synthesizes：
Using the gas containing nitrous acid ester and carbon monoxide as raw material generation oxidation and carbonylation synthesis of oxalate, the one of generation
Nitrogen oxide carries out nitrous acid ester regenerative response, obtains the chemical waste liquid of containing alcohol and dust technology and containing nitric oxide production synthesis circulation
Gas；Regenerative response is as follows：
4ROH+4NO+O2=4RONO+2H2O (I)
4NO+3O2+2H2O=4HNO3 (II)
Wherein formula (I) is nitrate regenerative response formula, and formula (II) is side reaction, and R represents CH3Or C2H5。
Waste liquid nitric acid treatment：
(1) caused chemical waste liquid in said process is heated to 75 DEG C through feed preheater 2, added from tower top, liquid air
Speed is 1.5h-1；Caused synthetic cyclic gas enters through valve 4 from the bottom of mixing column 1 during above-mentioned oxidative carbonylation, gas phase air speed
500h-1, reactor pressure 0.3Mpa；Tower bottoms is heated to 90~100 DEG C through feed preheater 2, is filled out from stainless steel metal ripple
Material top sprays and heated is heated to 85 DEG C into tower reaction gas, reaction gas through tower bottoms, enters catalyst layer from filler bottom；Make
Gas is obtained with liquid in beds counter current contacting；The catalyst bed temperature control is at 80 DEG C~90 DEG C.
The chemical waste liquid after measured, containing (mass fraction) nitric acid 1.5% and methanol 57%, water 41.5%.
After measured, concrete composition (percent by volume) is as follows for the synthetic cyclic gas：Nitric oxide 16%, methyl nitrite
4%th, carbon monoxide 12%, carbon dioxide 10%, methanol 8% and nitrogen 50%.
(2) reacted liquid phase mixes with tower reactor circulation fluid on tower tray, is sent to through tower reactor circulating pump 3 and out-of-bounds goes methanol to return
Receipts system.
(3) reaction raw materials of the liquid phase after Methanol Recovery is handled as oxalate, oxidative carbonylation system is put into again.
(4) synthetic cyclic gas is after catalyst layer contacts with reaction solution, by about 90% nitrate reductase in reaction solution, after reaction
Gas enters oxalic acid Lipase absobed through tower top valve 3.
In the present embodiment, other conditions are constant, and gas phase air speed only is adjusted into 1000h-1When, about 93% nitre in reaction also
Acid is reduced.
The oxidative carbonylation synthesis of oxalate of embodiment 3
The carbon-supported catalysts that the present embodiment uses specially cover carbon stainless steel wire packing for carbon attachment material；The carbon
Attachment material includes matrix and is covered in the carbon material layer of stromal surface.The carbon material layer is loose structure, including quality point
The powdered carbon of number 85%~90%, 10%~15% tar and 0.1%~0.3% auxiliary agent platinum.
The matrix is stainless steel cloth filler.
The carbon-supported catalysts are prepared as follows：
A, the powdered carbon of formula rate, blended tars are heated to 150 DEG C, stir to form carbon material dispersion liquid；
B, stainless steel cloth is handled 1 to 3 minute with 100 DEG C of 20% salpeter solution, rinsed to neutrality, then 3% hydrogen-oxygen
Change 80 DEG C of potassium solution to handle 15 minutes, the stainless steel cloth filler handled well is submerged into above-mentioned dispersion liquid, impregnated 0.5 hour
After take out and drain 2h so that carbon material, which is scattered in, is uniformly attached to stainless steel cloth filler surface, and it is multiple to obtain carbon material-matrix
It is fit；
C, the carbon material-substrate complex is completely cut off into air roasting 3h at 600~650 DEG C, then nitrogen protection declines
To normal temperature, by 30gPt/m3The materials of filler are than dipping platinum acid chloride solution, then will be dried under 120 DEG C of nitrogen protections of the stainless steel helices
Dry 2h, is then warming up to 200 DEG C of catalyst that this example is obtained with hydrogeneous 10% hydrogen and nitrogen gas small reductase 12 hour.
The technological process that this example uses, accompanying drawing 3 is referred in waste liquid nitric acid treatment part, is two tower process, and a tower is packed tower
4, built-in stainless steel cloth filler.Two towers are reaction tower 5, and filler is covers carbon stainless steel wire packing catalyst, point three sections of fillings.
The present embodiment flow is shown in Fig. 3：
Oxidative carbonylation synthesizes：
Oxidation and carbonylation synthesis of oxalate is occurred as raw material using the liquid containing nitrous acid ester and the gas containing carbon monoxide,
The nitric oxide of generation carries out nitrous acid ester regenerative response, obtains the chemical waste liquid of containing alcohol and dust technology and containing nitric oxide production
Synthetic cyclic gas；Regenerative response is as follows：
4ROH+4NO+O2=4RONO+2H2O (I)
4NO+3O2+2H2O=4HNO3 (II)
Wherein formula (I) is nitrate regenerative response formula, and formula (II) is side reaction, and R represents CH3Or C2H5。
Waste liquid nitric acid treatment：
(1) caused chemical waste liquid in said process is heated to 75 DEG C through feed preheater 2, added from the tower top of reaction tower 5
Enter, liquid air speed is 1.5h-1；The caused bottom of synthetic cyclic gas packed tower 4 enters during above-mentioned oxidative carbonylation, gas phase air speed
3000h-1(in relative response tower 5 for catalyst volume)；Tower bottoms is heated to 90~105 DEG C through feed preheater 2, from filler
The top tray of tower 4 is sprayed and heated into tower reaction gas；Reaction gas is preheating to 80 DEG C through the tower bottoms of packed tower 4, from the bottom of reaction tower 5
Into catalyst layer, the tower top pressure of reaction tower 5 is 1.5Mpa；So that gas and liquid are in beds counter current contacting；It is described
Catalyst bed temperature is controlled at 85~95 DEG C
The chemical waste liquid after measured, containing (mass fraction) nitric acid 8.5% and methanol 45.5%, water 46%.
After measured, concrete composition (percent by volume) is as follows for the synthetic cyclic gas：Nitric oxide 3%, methyl nitrite
7%th, carbon monoxide 22%, carbon dioxide 10%, methanol 8% and nitrogen 50%
(2) tower bottoms of reaction tower 5 is mixed with the tower top of packed tower 4 is pumped to the tower reactor circulation fluid of packed tower 4 on tower tray；
The another tower bottoms of packed tower 4 is sent through the part of tower reactor circulating pump 3 out-of-bounds goes methanol recovery system.
(3) reaction raw materials of the liquid phase after Methanol Recovery is handled as oxalate, oxidative carbonylation system is put into again.
(4) synthetic cyclic gas is after catalyst layer contacts with reaction solution, by about 98% nitrate reductase in reaction solution, after reaction
Gas enters oxalic acid Lipase absobed through the tower top valve 6 of packed tower 4.
The oxidative carbonylation synthesis of oxalate of embodiment 4
The carbon-supported catalysts that the present embodiment uses specially cover carbon plastic filler for carbon attachment material；The carbon adheres to material
Material includes matrix and is covered in the carbon material layer of stromal surface.The carbon material layer is loose structure, including mass fraction 95%
~98% active carbon powder and 2%~5% epoxy resin.
The matrix is plastic filler.
The carbon-supported catalysts are prepared as follows：
A, by active carbon powder nitrogen dispersion；
B, it will be submerged into the plastic filler after acetone treatment 3~5 minutes in epoxy adhesive, treat that plastic filler soaks
Stain is taken out after 0.5 hour and drained 10 minutes, blows to the activated carbon powder of 200~400 mesh with nitrogen and above-mentioned scribbles binding agent
Plastic filler surface, formed on filler surface and cover carbon-coating, obtain carbon material-substrate complex；
C, the carbon material-substrate complex is solidified into 2h under the conditions of 60 DEG C~80 DEG C, that is, obtains the catalysis of this example
Agent.
The technological process that this example uses, nitric acid treatment part refers to accompanying drawing 2, reactor, tower epimere is used as using mixing column 1
For sizer, filler is that catalyst covers carbon plastic filler catalyst, point three sections of fillings；Hypomere is plate column.
The present embodiment flow is shown in Fig. 2：
Oxidative carbonylation synthesizes：
Oxidation and carbonylation synthesis of oxalate is occurred as raw material using the liquid containing nitrous acid ester and the gas containing carbon monoxide,
The nitric oxide of generation carries out nitrous acid ester regenerative response, obtains the chemical waste liquid of containing alcohol and dust technology and containing nitric oxide production
Synthetic cyclic gas；Regenerative response is as follows：
4ROH+4NO+O2=4RONO+2H2O (I)
4NO+3O2+2H2O=4HNO3 (II)
Wherein formula (I) is nitrate regenerative response formula, and formula (II) is side reaction, and R represents CH3Or C2H5。
Waste liquid nitric acid treatment：
(1) caused chemical waste liquid in said process is heated to 70 DEG C through feed preheater 2, added from the tower top of mixing column 1
Enter, liquid air speed is 1.0h-1；Caused synthetic cyclic gas enters from the bottom of mixing column 1 during above-mentioned oxidative carbonylation, gas phase air speed
500h-1, reactor pressure 0.5Mpa；Tower bottoms is heated to 90~100 DEG C through feed preheater, from upper tray spray heat into
Tower reaction gas, reaction gas are preheating to 60 DEG C through tower bottoms, enter catalyst layer from packing layer top；So that gas is being urged with liquid
Agent bed current contacting；The catalyst bed temperature control is at 80 DEG C~85 DEG C.
The chemical waste liquid after measured, containing (mass fraction) nitric acid 2.5% and methanol 55%, water 41.5%.
After measured, concrete composition (percent by volume) is as follows for the synthetic cyclic gas：Nitric oxide 20%, methyl nitrite
2%th, carbon monoxide 10%, carbon dioxide 5%, methanol 8% and nitrogen 55%.
(2) reacted liquid phase mixes with tower reactor circulation fluid on tower tray, is sent through tower reactor circulating pump 3 and out-of-bounds goes Methanol Recovery
System.
(3) reaction raw materials of the liquid phase after Methanol Recovery is handled as oxalate, oxidative carbonylation system is put into again.
(4) synthetic cyclic gas is after catalyst layer contacts with reaction solution, by about 95% nitrate reductase in reaction solution, after reaction
Gas goes oxalate to synthesize through tower top valve 3.
The oxidative carbonylation synthesis of oxalate of embodiment 5
The carbon-supported catalysts that the present embodiment uses specially cover carbon stainless steel mellapak packing for carbon attachment material；It is described
Carbon attachment material includes matrix and is covered in the carbon material layer of stromal surface.The carbon material layer is loose structure, including quality
The powdered carbon of fraction 87%~93%, 7%~13% tar.
The matrix position stainless steel plate ripple packing
The carbon-supported catalysts are prepared as follows：
A, the powdered carbon of formula rate, blended tars are heated to 150 DEG C, stir to form carbon material dispersion liquid；
B, handle stainless steel plate ripple packing 4~6 minutes with 20% salpeter solution, rinsed with water to neutrality, then 3% hydrogen
80 DEG C of potassium oxide solution is handled 30 minutes, and the stainless steel helices handled well is submerged into above-mentioned carbon material dispersion liquid, treated stainless
Taken out after steel filler dipping 5~10 and drain 2h, obtain carbon material-substrate complex；
C, the carbon material-substrate complex is completely cut off into air roasting 3h 600 DEG C~650, be down under nitrogen protection
Normal temperature
Repetition walks the above-mentioned catalyst for covering carbon process 2~3 times, that is, obtaining this example.
Accompanying drawing 3 is referred in the technological process that the present embodiment uses, nitric acid treatment part, and a tower is packed tower 4, and built-in ceramics are filled out
Material, two towers are reaction tower 5, built with carbon stainless steel mellapak packing catalyst is covered, divide three sections of fillings.
The present embodiment flow is shown in Fig. 3
Oxidative carbonylation synthesizes：
Oxidation and carbonylation synthesis of oxalate is occurred as raw material using the liquid containing nitrous acid ester and the gas containing carbon monoxide,
The nitric oxide of generation carries out nitrous acid ester regenerative response, obtains the chemical waste liquid of containing alcohol and dust technology and containing nitric oxide production
Synthetic cyclic gas；Regenerative response is as follows：
4ROH+4NO+O2=4RONO+2H2O (I)
4NO+3O2+2H2O=4HNO3 (II)
Wherein formula (I) is nitrate regenerative response formula, and formula (II) is side reaction, and R represents CH3Or C2H5。
Waste liquid nitric acid treatment：
(1) by caused chemical waste liquid in said process after feed preheater 2 is heated to 80 DEG C, from the tower top of reaction tower 5
Beds are sprayed, liquid air speed is 3h-1；Caused synthetic cyclic gas is from the bottom of packed tower 4 during above-mentioned oxidative carbonylation
Into gas phase air speed 100h-1(in relative response tower 2 for catalyst volume)；The heated device of the kettle liquid of packed tower 1 is heated to 90~
100 DEG C, spray and heat into tower reaction gas from the middle and upper part column plate of packed tower 4, reaction gas is preheating to 85 DEG C；Reaction after heating
Gas enters beds from the top of reaction tower 5 so that gas is with liquid in beds current contacting；The catalyst bed
Temperature control is at 90 DEG C~95 DEG C.
The chemical waste liquid after measured, containing (mass fraction) nitric acid 1.0% and methanol 60%, water 39%.
After measured, concrete composition (percent by volume) is as follows for the synthetic cyclic gas：Nitric oxide 15%, methyl nitrite
5%th, carbon monoxide 12%, carbon dioxide 10%, methanol 8% and nitrogen 50%.
(2) the tower bottoms tower reactor circulating pump 3 of reaction tower 5 delivers to the tower top of packed tower 4, with the tower reactor circulation fluid of packed tower 4 in tower
Mixed on disk；The another tower bottoms of packed tower 1 is sent through the part of tower reactor pump 2 out-of-bounds goes methanol recovery system.
(3) reaction raw materials of the liquid phase after Methanol Recovery is handled as oxalate, oxidative carbonylation system is put into again.
(4) synthetic cyclic gas is after catalyst layer contacts with reaction solution, by about 90% nitrate reductase in reaction solution, after reaction
Gas goes oxalate to synthesize through tower top valve 6.
The nitric acid treatment flow of embodiment 1 to 5 is also suitable for oxidative carbonylation synthesizing carbonate ester, the methanol in embodiment 1 to 5
Also can be replaced by ethanol.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, all any modification, equivalent and improvement made within the spirit and principles of the invention etc., all should be included
Within protection scope of the present invention.
Claims (9)
1. a kind of catalyst of oxidative carbonylation synthesis liquid waste processing, it is characterised in that be carbon attachment material；The carbon attachment
Material includes matrix and is covered in the carbon material layer of stromal surface；The carbon material layer is loose structure, the carbon material layer by
The carbon material of mass fraction 85%~98%, 2%~15% binding agent and 0.1%~10% auxiliary agent composition, the auxiliary agent are
B, or Pt；The matrix is tower structured packing or random packing.
2. catalyst as claimed in claim 1, it is characterised in that the binding agent is tar or epoxy resin；The matrix
For ceramics, stainless steel and/or plastic material.
3. the preparation method of catalyst as claimed in claim 1 or 2, it is characterised in that comprise the following steps：
A, by carbon material carry out it is scattered form dispersion, using gas dispersion air is scattered or liquid dispersion, by carbon material and
Dispersant, binding agent are uniformly mixed to form carbon material dispersion liquid；
B, the carbon material dispersion obtained in step A is uniformly attached to stromal surface, obtains carbon material-substrate complex；
C, the carbon material obtained in step B-substrate complex is subjected to attached shape processing, obtains carbon-supported catalysts；At the attached shape
Reason includes drying, roasting, and/or activation process.
4. a kind of oxidative carbonylation synthesis technique, it is characterised in that comprise the following steps：
Oxidative carbonylation synthesizes：Oxidation and carbonylation is occurred as raw material using the liquid containing nitrous acid ester and the gas containing carbon monoxide
Synthesis, the nitric oxide of generation carry out nitrous acid ester regenerative response, obtain the chemical waste liquid of containing alcohol and dust technology and containing an oxygen
Change the synthetic cyclic gas of nitrogen；
Waste liquid nitric acid treatment：
(1) by the caused chemical waste liquid containing alcohol and dust technology in oxidative carbonylation synthetic reaction with containing nitric oxide production synthesis
Circulating air, cocurrent or countercurrent pass through catalyst bed, the liquid and gas after being handled；
(2) alcohol in the liquid phase after the processing obtained in recycling step (1), obtains the liquid phase after dealcoholysis；
(3) liquid phase after the dealcoholysis that will be obtained in step (2) is thrown as the liquid charging stock containing nitrous acid ester that oxidative carbonylation synthesizes
Enter；
(4) gas phase after the processing that will be obtained in step (1), it is former with the gas containing carbon monoxide to put into the oxidative carbonylation synthesis
Material；
The catalyst bed, the catalyst of filling is activated carbon or the catalyst as described in right wants 1 or 2.
5. oxidative carbonylation synthesis technique as claimed in claim 4, it is characterised in that the chemical waste liquid, wherein nitric acid are dense
Degree is less than or equal to 10%；The synthetic cyclic gas, wherein nitric oxide production percent by volume is between 1% to 20%.
6. oxidative carbonylation synthesis technique as claimed in claim 4, it is characterised in that the chemical waste liquid and synthetic cyclic gas
By preheating.
7. oxidative carbonylation synthesis technique as claimed in claim 4, it is characterised in that pass through catalyst bed when using cocurrent
When, the chemical waste liquid and synthetic cyclic gas are by premix.
8. oxidative carbonylation synthesis technique as claimed in claim 4, it is characterised in that cocurrent or countercurrent passes through catalyst bed
When, wherein liquid phase air speed is in 0.1h-1~3h-1Between, gas phase air speed is in 100h-1~3000h-1Between.
9. oxidative carbonylation synthesis technique as claimed in claim 4, it is characterised in that the catalyst bed temperature control is 30
Between~120 DEG C, reaction pressure is in 0.1Mpa between 1.50Mpa.
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