CN107963999A - The method that vpo catalyst auxiliary agent water addition is controlled in MAH preparation process - Google Patents

The method that vpo catalyst auxiliary agent water addition is controlled in MAH preparation process Download PDF

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CN107963999A
CN107963999A CN201610911360.6A CN201610911360A CN107963999A CN 107963999 A CN107963999 A CN 107963999A CN 201610911360 A CN201610911360 A CN 201610911360A CN 107963999 A CN107963999 A CN 107963999A
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msub
auxiliary agent
water
mah
reactor
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CN107963999B (en
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杨效军
陈志明
李剑
杨如惠
张威
赵东
赵东一
眭伟华
徐星宇
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China Petroleum and Chemical Corp
Sinopec Yizheng Chemical Fibre Co Ltd
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China Petroleum and Chemical Corp
Sinopec Yizheng Chemical Fibre Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/60—Two oxygen atoms, e.g. succinic anhydride

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The present invention relates to a kind of method that vpo catalyst auxiliary agent water addition is controlled in MAH preparation process, it is characterised in that：On the water control valve that the tube-shell type fixed bed reactor for preparing MAH connects, Atmosphere And Humidity instrument and computing module are connected, by Atmosphere temp.and RH instrument measuring environment temperature T, relative humidity RH, surveyed numerical value is inputted into computing module, calculated by formula, the accurate addition for controlling auxiliary agent water.The present invention realizes the accurate control for adding catalyst bed auxiliary agent water, the humidity into the butane mixture gase of reactor is maintained at steady state value, from the influence of the humiture of environment；The high selectivity and yield of catalyst are improved, selectively improves 2.1%, mass yield improves 2.4%, avoids：Because adding the too low temperature distributing disproportionation for causing phosphide to concentrate on reactor feed end, making reactor of water, and moisture adds and excessive causes accessory substance to increase.

Description

The method that vpo catalyst auxiliary agent water addition is controlled in MAH preparation process
Technical field
The present invention relates to the hydrocarbon catalyticing oxidation field of more than 4 carbon atoms, and in particular to is produced by raw material of normal butane The accuracy control method of catalyst promoter water addition during cis-butenedioic anhydride.
Background technology
Cis-butenedioic anhydride (MAH) is a kind of common basic organic chemical industry raw material, is the second largest acid anhydrides for being only second to phthalic anhydride in the world Raw material, and product has quite extensive development and application prospect downstream.MAH is widely used in synthetic resin, and lubricating oil adds Add agent, medicine, food additives, 1,4 butanediols, gamma butyrolactone, tetrahydrofuran, succinic acid, fumaric acid etc. a series of important Organic chemicals and fine chemicals.
N butane oxidation method produces MAH, is with vanadium phosphorus oxygen (VPO) catalyst or the vpo catalyst containing a small amount of auxiliary agent, example Such as：Contain molybdenum, zinc, uranium, tungsten, tin, bismuth, titanium, niobium, antimony and cobalt etc..On tube-shell type fixed bed reactor, temperature 400-450 React under the conditions of DEG C, which is strongly exothermic, contains product MAH and accessory substance acetic acid, propylene in reaction generation gas Acid, carbon monoxide and carbon dioxide.The heat that reaction produces is taken away heat by the fused salt of flowing.Fixed bed reactors at present The draw ratio of tubulation greatly above 100, the cooling capacity of fused salt is substantially consistent in whole reactor, but reaction rate Change with the concentration of normal butane and the temperature change of catalyst bed, since normal butane mixed gas enters reactor bottom Temperature it is relatively low, with the initiation of reaction, reaction rate is getting faster, until butane concentration reduce slow down exothermic heat of reaction.Instead Should most acutely, heat release at most makes the highest point of reaction bed temperature be known as hot(test)-spot temperature, and hot(test)-spot temperature is higher, generates accessory substance More, conversion ratio is more lower in high yield, and selectivity declines.If hot(test)-spot temperature is more than 500 DEG C, or highest hot(test)-spot temperature and fused salt Temperature difference exceeds 60 DEG C, and catalyst can inactivate, the lost of life of catalyst.
In order to improve catalyst choice, reduce activity and improve yield, phosphide, such as phosphorus are usually added into the art Sour trimethyl or triethyl phosphate adjust the activity and selectivity of catalyst.The main function of supplement phosphorus is to maintain VPO catalysis Phosphorus vanadium ratio in agent, maintains the active phase (VO) of generation MAH2P2O7Ratio in the catalyst.After supplementing phosphide, interruption Or auxiliary agent water is continuously added into, the phosphide of addition is more uniformly distributed on the catalyst bed.H.W.Zanthoff is in document (On the active role of water during partial oxidation of n-butane to maleic anhydride over(VO)2P2O7Catalysts [J] .Applied Catalysts, 1998,172 (1):49-58) point out, Water is at (VO)2P2O7Play an important role during active phase catalyst catalysis oxidation normal butane MAH.On the one hand, water can be with Suppress nonactive Irreversible Adsorption of the normal butane on vpo catalyst, improve the desorption rate of reaction product；On the other hand, Absorption on water decomposition vpo catalyst is broken V-O-V, V-O-P, or P-O-P key, promotes the generation of V-OH and P-OH groups, Such a structure makes redox reaction more easily carry out, so that catalyst is in high activity state when generating MAH.
Existing patent US4701433 and patent US4810803, which are disclosed, introduces water and phosphide to MAH reactor catalysts Bed, with partial inactivation catalyst, makes the downward downstream of hot spot, produces hot spot region deactivation before making, and make reactor more Isothermal is added to be distributed, so as to improve MAH yields.Phosphorus compound is to include alkyl phosphate and alkylphosphonic, including tripotassium phosphate Ester.It is that 0.005-5g/Kg catalyst is daily that patent, which describes phosphide addition, and the addition of water is the 0.1- of mixed gas quality 4wt%, after trimethyl phosphate and water add, the downward downstream of hot(test)-spot temperature, improves the selectivity and yield of catalyst.But It is that phosphide and water is not when the mode for adding or adding describes.The addition that patent only describes water is gaseous mixture The 0.1-4% of quality, does not mention the humidity for how stablizing gaseous mixture, to ensure the best selective of catalyst.
Patent US4515899 describes water treatment phosphorus processing vpo catalyst, the method for improving yield.The patent is pointed out, is used Phosphide handles catalyst degradation activity but improves selectivity, and active loss is by improving reaction temperature compensation.The patent It was found that phosphorus compound concentration is near reactor feed end, thus it requires wanting the addition of phosphorus restriction.Add after being handled with phosphide Water makes phosphorus compound more uniformly redistribute in whole reaction zone.Water, which adds, to handle a period of time afterwards in phosphide, Water can also be added immediately.Selected phosphide is Trimethyl phosphite and trimethyl phosphate in the method for the patent.This is special Sharp technology improves the selectivity and yield of catalyst, but and undeclared water by using water process after adding trimethyl phosphate Control Adding Way and addition, and influence of the air humidity to catalyst performance itself.
The content of the invention
The purpose of the present invention overcomes the above problem existing in the prior art, there is provided controls VPO to urge in a kind of MAH preparation process The method of agent auxiliary agent water addition, can accurately control addition auxiliary agent water, make into the wet of the butane mixture gase of reactor Degree is maintained at steady state value, from the influence of the humiture of environment, improves the selectivity and yield of vpo catalyst.
The purpose of the present invention is achieved through the following technical solutions：Vpo catalyst auxiliary agent is controlled in a kind of MAH preparation process The method of water addition, on the water control valve that the tube-shell type fixed bed reactor for preparing MAH connects, connects Atmosphere And Humidity instrument and meter Control module is calculated, by Atmosphere temp.and RH instrument measuring environment temperature T, relative humidity RH, surveyed numerical value is inputted into calculation control module, Calculated by formula, the accurate addition for controlling auxiliary agent water；Its calculation formula is：
Wherein, m3It is to remove the water that the moisture in air supplements afterwards, which changes and change with Atmosphere temp.and RH, m3 To add the mass flow t/h of water in reactor；RH is current atmospheric relative humidity %；C3For the water concentration mol% of gaseous mixture； T is current atmospheric temperature DEG C；m1To enter the air quality flow of reactor；m2For butane mass flow t/h；SV is by anti- Answer the air speed h of device-1；V is the volume m of catalyst3；M1For air relative atomic weight, value 29；M2For butane relative atomic weight, take Value 58；M3For the relative atomic weight of water, value 18；A value ranges are that 3~50, b value ranges are 0.1~20.
Further, the atmospheric temperature excursion is between -50 to 50 DEG C.
Further, the vpo catalyst meets following formula：
(VO)2P2O7·A·B；
Wherein, A VOPO4、VO(PO3)2、VO(H2PO4)、VO(HPO4)·0.5H2O、VO(HPO4)2H2O、(VO)2H4P2O9 In one or more combination；
B for Fe, Co, Zr, Ni, W, Cd, Bi, Li, Hf, Mo, B, Si, U, Ba, In, Pd, Cu, Mn, Cr, Zn, Sn, Ce, Sm, One or more in I, II race element and its one or more combination in oxide in Th, Nd, Y and the periodic table of elements.
Further, in the vpo catalyst average valence of vanadium between+4 to+4.5.
Further, it is described to add water m3The molar concentration scope for accounting for gaseous mixture is 0~5mol%.
Further, the value range of a is that 3~50, b value ranges are 0.1~20 in the formula.
Yet further, the humiture instrument number used is at least 1.
The substantive distinguishing features and significant progress of the protrusion of technical solution of the present invention are mainly reflected in：The present invention realizes The accurate control of catalyst bed auxiliary agent water is added in MAH preparation process, makes the humidity into the butane mixture gase of reactor Steady state value is maintained at, from the influence of the humiture of environment；Avoid that water is too low causes phosphide to concentrate on reaction because adding Device feed end, makes the temperature distributing disproportionation of reactor, and moisture addition excessively cause accessory substance to increase, such as maleic acid, rich horse Acid, phthalic acid mono-n-butylester etc.；The high selectivity and yield of catalyst are improved, selectively improves 2.1%, mass yield Improve 2.4%.
Brief description of the drawings
Fig. 1 is the process flow chart that MAH is prepared using the method for the invention；Wherein mark meaning is：A- humiture instruments, B- calculation control modules, 1- water, 2- Water flow control valves, 3- air, 4- butagas, 5- phosphides add device, the storage of 6- phosphides Tank, 7- fixed bed reactors, 8- phosphide atomizers, 9- mixers.
Fig. 2 is the existing process flow chart for preparing MAH；Wherein mark meaning is：1- water, 2- Water flow control valves, 3- are empty Gas, 4- butagas, 5- phosphate add device, 6- phosphide storage tanks, 7- fixed bed reactors, 8- phosphide atomizers, 9- mixing Device, 10- flow controllers.
Embodiment
Water plays an important role during normal butane cis-butenedioic anhydride (MAH), on the one hand, water enters anti-as a vapor Device bottom is answered, bottom is contacted to phosphide unnecessary on the catalyst of phosphide at first and takes away and is distributed in catalyst bed again Layer, will not make catalyst excessively lose activity because phosphide is excessively attached to catalyst surface；On the other hand, can suppress just Nonactive Irreversible Adsorption of the butane on vpo catalyst, improves the desorption rate of reaction product, so that catalyst is in life Into being in high selectivity state during MAH.
Water is added without accurate control in the prior art, stablizes the method for gaseous mixture humidity, to solve in MAH productions, into Enter the humidity of the butane mixture gase of reactor is influenced by atmospheric temperature and humidity, declines the selectivity of catalyst.This Invention provides a kind of method that vpo catalyst auxiliary agent water addition is controlled in MAH preparation process, accurately addition can be controlled to help The water of agent, makes the humidity of butane mixture gase into reactor be maintained at steady state value, from the influence of the humiture of environment, from And making phosphide be unlikely to concentrate on reactor feed end, the temperature of reactor is uniformly distributed, conjunction of the hot spot in catalyst bed Position is managed, with having reached high catalyst selectivity, mesh in high yield.
Humidity into the butane mixture gase of reactor is influenced by atmospheric temperature and humidity.Add that water is too low leads Phosphide is caused to concentrate on reactor feed end, the temperature distributing disproportionation of reactor；Moisture, which adds, excessively causes accessory substance to increase, such as Maleic acid, fumaric acid, phthalic acid mono-n-butylester etc..
Therefore, inventor is by the water control valve of tube-shell type fixed bed reactor connection for preparing MAH, connecting Atmosphere And Humidity instrument and calculation control module, by Atmosphere temp.and RH instrument measuring environment temperature T, relative humidity RH, numerical value input calculates Control module, is calculated by formula, the accurate addition for controlling auxiliary agent water；Its calculation formula is：
Calculating addition water is to measure environment temperature T, relative humidity RH by humiture instrument, and numerical value is conveyed to computer Calculate, then automatic assignment feed water brake door is adjusted, and addition water changes and changes with ambient temperature and humidity, ensures The stabilization of humidity in butane mixture gase, so as to fulfill the accurate control of water and butane mixture gase humidity is added.VPO is improved to urge The selectivity of agent, improves the yield of MAH.M in formula3It is current atmospheric to add the mass flow t/h, RH of catalyst water Relative humidity %, C3For the water concentration mol% of gaseous mixture；T current atmospheric temperatures DEG C, atmospheric temperature excursion is -50 To between 50 DEG C；m1To enter the air quality flow of reactor, m2Butane mass flow t/h, SV are the air speed by reactor h-1, V is the volume m of catalyst3, M1For air relative atomic weight 29, M2For butane relative atomic weight 58, M3For the relatively former of water Son amount, value 18, a value ranges are that 3~50, b value ranges are 0.1~20.
Preceding method is suitable for vpo catalyst, which meets following formula：(VO)2P2O7·A·B；
Wherein, A VOPO4、VO(PO3)2、VO(H2PO4)、VO(HPO4)·0.5H2O、VO(HPO4)2H2O、(VO)2H4P2O9 In one or more combination, B Fe, Co, Zr, Ni, W, Cd, Bi, Li, Hf, Mo, B, Si, U, Ba, In, Pd, Cu, Mn, Cr, One or more in Zn, Sn, Ce, Sm, Th, Nd, Y and the periodic table of elements in I, II race element and its one kind in oxide or Several combinations.
Preferably, the average valence of vanadium is between+4 to+4.5 in the vpo catalyst for preceding method；Need to add water Measure m3The molar concentration scope for accounting for gaseous mixture is 0-5mol%；The value range of a is the value range of 3~50, b in above-mentioned formula For 0.1~20；The humiture instrument is at least 1 using number.
Technical solution of the present invention is applied to prepare the technological process of MAH, as shown in Figure 1, being prepared with traditional MAH Process unit compare, using the present invention method process unit Water flow control valve 2 successively with calculation control module B and Humiture instrument A is connected.Humiture instrument A, which measures environment temperature and relative humidity and calculates water vapour by calculation control module B, to be added Enter amount m3, by adjust vapor flow control valve 2 control into reactor 7 flow, 5 mixing of butagas 4 and phosphide Mixed afterwards with air 3,1 addition point of vapor is located at before gaseous mixture, which is the water content removed in air, with humiture Instrument changes and changes, and ensure that the stabilization of butane mixture gase humidity.
The present invention realizes the accurate control for adding catalyst bed auxiliary agent water, makes the butane mixture gase into reactor Humidity be maintained at steady state value, from the influence of the humiture of environment.Avoid that water is too low causes phosphide to concentrate on because adding Reactor feed end, the temperature distributing disproportionation of reactor；Moisture add it is excessive cause accessory substance to increase, as maleic acid, fumaric acid, Phthalic acid mono-n-butylester etc..The high selectivity and yield of catalysis are improved, selectively improves 2.1%, mass yield improves 2.4%.
Technical solution of the present invention is specifically illustrated below in conjunction with specific embodiment, but this is the excellent of the present invention Select embodiment, it is noted that for those skilled in the art, do not departing from the technology of the present invention principle Under the premise of, can also make some improvement and modification, these improvements and modifications should also be considered as protection scope of the present invention it It is interior.
Comparative example
In 120,000 tons/year of MAH process units that HUNSTMAN technologies provide, normal butane in tube-shell type fixed bed reactor, Under vpo catalyst existence condition, catalyst bed layer height 5900mm, catalyst tubulation diameter 25mm, butane concentration 1.85mol%, air speed 1560h-1, trimethyl phosphate (TMP) input concentration 8ppm, reactor inlet pressure 180Kpag, by Fig. 2 Flow controller maintain water charging 800kg/h it is constant.Catalyst run from 1800 to 1848 it is small when after, conversion ratio by 83.5% is increased to 83.9%, and selectivity 67.9% is down to 66.9%, and mass yield is from 95.8% to 94.9%；Run to 1896 Hour conversion ratio 83.6%, selectivity 67.5%, mass yield 95.4%.
Embodiment
In 120,000 tons/year of MAH process units that HUNSTMAN technologies provide, normal butane is in tube-shell type fixed bed reaction Device, under vpo catalyst existence condition, catalyst bed layer height 5900mm, catalyst tubulation diameter 25mm, butane concentration 1.85mol%, air speed 1560h-1, trimethyl phosphate (TMP) 8ppm, reactor inlet pressure 180Kpag, using work shown in Fig. 1 Skill flow adds water, ensures that water concentration 2.4mol% is constant in gaseous mixture.Catalyst run to 1935 it is small when, conversion ratio is 83.2%, mass yield 98.2%, selectivity 70%；Operation to 1983 it is small when conversion ratio be 83.2%, mass yield 98.2%, Selectivity 70%；Operation to 2031 it is small when, conversion ratio 83.2%, mass yield 98.2%, selectivity 70%.
In conclusion the present invention uses humiture instrument measuring environment temperature T, relative humidity RH, calculated away by formula Except the amount for needing to maintain the certain humidity of gaseous mixture to require supplementation with moisture after water content in air, this method can accurately control entrance The water of reactor, stablizes the humidity of butane mixture gase, stablizes the addition of water and continues.Avoid makes instead because adding hypervolia Accessory substance maleic acid in product is answered to increase, it is too low to add water, can make the phosphide of addition skewness on a catalyst, Cause catalyst member passivation serious, it is amount of activated higher.The accurate control of addition water amount is realized, and with ambient temperature and humidity Change adjusted in real time.

Claims (7)

1. the method for vpo catalyst auxiliary agent water addition is controlled in a kind of MAH preparation process, it is characterised in that：Preparing MAH's On the water control valve of tube-shell type fixed bed reactor connection, Atmosphere And Humidity instrument and calculation control module are connected, by Atmosphere temp.and RH instrument Measuring environment temperature T, relative humidity RH, input calculation control module by surveyed numerical value, are calculated by formula, accurate to control auxiliary agent water Addition；Its calculation formula is：
<mrow> <msub> <mi>m</mi> <mn>3</mn> </msub> <mo>=</mo> <mrow> <mo>(</mo> <mfrac> <msub> <mi>m</mi> <mn>1</mn> </msub> <msub> <mi>M</mi> <mn>1</mn> </msub> </mfrac> <mo>+</mo> <mfrac> <msub> <mi>m</mi> <mn>2</mn> </msub> <msub> <mi>M</mi> <mn>2</mn> </msub> </mfrac> <mo>)</mo> </mrow> <mo>&amp;times;</mo> <msub> <mi>C</mi> <mn>3</mn> </msub> <mo>&amp;times;</mo> <msub> <mi>M</mi> <mn>3</mn> </msub> <mo>-</mo> <mfrac> <mrow> <mo>(</mo> <mn>6.64</mn> <mo>&amp;times;</mo> <msup> <mi>e</mi> <mfrac> <mi>T</mi> <mi>a</mi> </mfrac> </msup> <mo>-</mo> <mi>b</mi> <mo>)</mo> <mo>&amp;times;</mo> <mi>R</mi> <mi>H</mi> <mo>&amp;times;</mo> <mi>S</mi> <mi>V</mi> <mo>&amp;times;</mo> <mi>V</mi> </mrow> <mn>1000</mn> </mfrac> </mrow>
Wherein, m3It is to remove the water that the moisture in air supplements afterwards, which changes and change with Atmosphere temp.and RH, m3To add Enter the mass flow t/h of water in reactor；RH is current atmospheric relative humidity %；C3For the water concentration mol% of gaseous mixture；T is Current atmospheric temperature DEG C；m1To enter the air quality flow of reactor；m2For butane mass flow t/h；SV is to pass through reactor Air speed h-1；V is the volume m of catalyst3；M1For air relative atomic weight, value 29；M2For butane relative atomic weight, value 58；M3For the relative atomic weight of water, value 18；A value ranges are that 3~50, b value ranges are 0.1~20.
2. controlling the method for vpo catalyst auxiliary agent water addition in MAH preparation process according to claim 1, its feature exists In：The atmospheric temperature excursion is between -50 to 50 DEG C.
3. controlling the method for vpo catalyst auxiliary agent water addition in MAH preparation process according to claim 1, its feature exists In：The vpo catalyst meets following formula：(VO)2P2O7·A·B
Wherein, A VOPO4、VO(PO3)2、VO(H2PO4)、VO(HPO4)·0.5H2O、VO(HPO4)2H2O、(VO)2H4P2O9In One or more combination；
B for Fe, Co, Zr, Ni, W, Cd, Bi, Li, Hf, Mo, B, Si, U, Ba, In, Pd, Cu, Mn, Cr, Zn, Sn, Ce, Sm, Th, One or more in I, II race element and its one or more combination in oxide in Nd, Y and the periodic table of elements.
4. controlling the method for vpo catalyst auxiliary agent water addition in MAH preparation process according to claim 3, its feature exists In：The average valence of vanadium is between+4 to+4.5 in the vpo catalyst.
5. controlling the method for vpo catalyst auxiliary agent water addition in MAH preparation process according to claim 1, its feature exists In：It is described to add water m3The molar concentration scope for accounting for gaseous mixture is 0~5mol%.
6. controlling the method for vpo catalyst auxiliary agent water addition in MAH preparation process according to claim 1, its feature exists In：The value range of a is that 3~50, b value ranges are 0.1~20 in the formula.
7. controlling the method for vpo catalyst auxiliary agent water addition in MAH preparation process according to claim 1, its feature exists In：The humiture instrument number used is at least 1.
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CN111883766A (en) * 2020-07-30 2020-11-03 西南大学 Polyanion electrode material and preparation method and application thereof
CN114682278A (en) * 2020-12-29 2022-07-01 中国石油化工股份有限公司 Anti-losing vanadium phosphorus oxygen catalyst

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Publication number Priority date Publication date Assignee Title
CN111883766A (en) * 2020-07-30 2020-11-03 西南大学 Polyanion electrode material and preparation method and application thereof
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CN114682278B (en) * 2020-12-29 2023-09-01 中国石油化工股份有限公司 Anti-phosphorus loss vanadium phosphorus oxide catalyst

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