CN103638951A - Catalyst for preparing acrylic acid through lactic acid dehydration and application thereof - Google Patents
Catalyst for preparing acrylic acid through lactic acid dehydration and application thereof Download PDFInfo
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- CN103638951A CN103638951A CN201310602822.2A CN201310602822A CN103638951A CN 103638951 A CN103638951 A CN 103638951A CN 201310602822 A CN201310602822 A CN 201310602822A CN 103638951 A CN103638951 A CN 103638951A
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Abstract
The invention discloses a catalyst for preparing acrylic acid through lactic acid dehydration. The catalyst is characterized by being obtained through the following steps: subjecting a soluble alkaline earth metal M salt solution or an alkaline earth metal M hydroxide solution to carry out reactions with dilute sulfuric acid or an alkaline metal sulfate solution so as to obtain alkaline earth metal sulfate, then allowing the solution to stand still for a while so as to precipitate the alkaline earth metal sulfate, filtering, washing the precipitation with distilled water, then drying the alkaline earth metal sulfate in a drying oven, putting the alkaline earth metal sulfate in a muffle furnace after the drying process, and calcining the alkaline earth metal sulfate by using a program to control and raise the temperature. The alkaline earth metal sulfate catalyst has the advantages of environment-friendliness, simple preparation, low cost, high catalytic activity, good stability, high acrylic acid selectivity, and high conversion rate of lactic acid, and has a potential commercial development value.
Description
Technical field
The invention belongs to chemical field, be specifically related to the new method with the sulfate catalysis crylic acid preparation by lactic acid dehydration of alkaline-earth metal.
Background technology
Acrylic acid is a kind of important unsaturated organic acid, and structural formula is H
2c=CH-COOH, is water white transparency shape liquid under normal temperature and pressure, can dissolve each other by arbitrary proportion with water.In acrylic acid structure formula, have a two key, also have a carboxyl, so chemical property is active, acidity is stronger.Acrylic acid major part is used to prepare acrylate, can homopolymerization or copolymerization between acrylates and ester, also can with the monomer copolymerization such as acrylonitrile, styrene, butadiene, vinyl chloride and cis-butenedioic anhydride, the polymer of formation is because the performance that has many excellences is extensively used to the fields such as synthetic resin, adhesive, synthetic rubber, synthetic fibers, super absorbent resin, pharmacy, leather, weaving, chemical fibre, building materials, water treatment, oil exploitation, coating as protected look, fast light, heat-resisting, resistance to oxidation, ageing-resistant, super-strong moisture absorbing etc.Along with the rapid progress of acrylic acid distillation technology, high-purity acrylic acid (glacial acrylic acid) is separated, and this type of acrylic acid is particularly suitable for for producing women and children's physiological hygiene articles for use.Visible acrylic acid is a kind of very important bulk chemical, is also one of important source material of industrial synthetic various high value added products simultaneously.Due to women and children's amenities and the dramatic growth of water-soluble building coating demand, so acrylic acid total quantity consumed in recent years is also rising year by year.
According to the recyclability of synthesizing propylene acid starting material, the process route of acrylic acid synthesizing mainly can be divided into two large classes, and bio-based route is as producing acroleic acid by lactic acid dewatering, dehydrating glycerin oxidation acrylic acid processed; Abiotic base route is as oxidation of propylene, propane oxidation, acetylene oxo synthesis.In these preparation methods, with acid by dehydrating lactic method, receive much concern, its reason is that this route is sustainable development route; By starchiness or cellulose, prepare lactic acid technology and reach its maturity, lactic origin is secure; High temperature gas phase crylic acid preparation by lactic acid dehydration has been obtained greater advance in recent years.The catalyst of crylic acid preparation by lactic acid dehydration mainly contains slaine, zeolite molecular sieve, heteropolyacid salt etc.The first kind: metallic salt catalyst, as CaSO
4, KHSO
4, K
2hPO
4, etc.Holmen[USP 2859240,1958] report in fixed-bed reactor that lactic acid is at Na
2sO
4/ CaSO
4under catalytic action, dewater, when lactic acid concn is 10wt%, during 400 ℃ of reaction temperatures, acrylic acid selectively reaches 68%.This catalyst is by certain density Na
2sO
4solution and ultra-fine CaSO
4powder mixes with the mol ratio slurry state shape of 1:25, then dry making.Sawicki[USP4729978,1988] with inorganic base, make pH adjusting agent, the catalyst making by phosphate solution metal oxide-impregnated carrier is for catalysis acid by dehydrating lactic.Experimental result is found, is first used sodium dihydrogen phosphate impregnation of silica carrier subsequent drying, then with Na
2cO
3after solution double-steeping, the dry catalyst reaction performance making is best again, and the high selectivity of acrylic acid is 65%, and corresponding rotational rate of lactic acid reaches 89%.In addition, the document also comparative study the reactivity worth of the catalyst prepared of the different oxide carriers such as silica, titanium dioxide or alchlor, best with silica supports.The people such as Paparizos [USP4786756A, 1988] under gas-solid reaction condition with the pretreated AlPO of inorganic base
4catalysis lactic acid or aqueous solution of ammonia lactate Dehydration acrylic acid, the ammonia spirit with 14wt% before charging purges 30min 340 ℃ of reaction temperatures to beds, and having obtained best acrylic acid yield is 61.1%, and in product, propionic acid content is also very little.Under Gunter etc. [Ind.Eng.Chem.Res, 34,974,1995] people, support type phosphate catalyst is for producing acroleic acid by lactic acid dewatering coproduction 2,3-pentanedione.Experiment discovery, the silica with low specific surface area is that the catalyst that carrier makes can suppress the generation such as side reactions such as decarbonylation decarboxylations.The generation of these side reactions is mainly owing to the high specific area of silica and the stronger acidic site in its surface.Best reaction condition and result: 300 ℃ of reaction temperatures, stagnation pressure 0.5MPa, take silicon dioxide carried natrium arsenicum during as catalyst experiment obtain the highest acrylic acid and 2,3-pentanedione overall selectivity reaches 83%, 2,3-pentanedione yield and reaches 25%.Tan Tianwei etc. [ZL:200810113126.4] have introduced the second-stage reaction process of being produced acrylic acid or acrylate by lactic acid or lactate.This patent of invention adopts two sections of vertical reactors, first preheating before top of lactic raw material, and two sections are filled respectively dissimilar catalyst, lower termination gas-liquid separator.When upper and lower two ends, filling 13X molecular sieve and praseodymium phosphate/calcium sulfate/copper sulphate complex salt while making catalyst respectively, the methyl lactate of 60wt% of take is raw material, and during 400 ℃ of reaction temperatures, catalytic effect is best, and acrylic acid is selectively up to 85%.Zhang etc. [The Canadian Journal of Chemical Engineering2008,86,1047] have studied under gas-solid phase condition with sulfate composite catalyst catalysis acid by dehydrating lactic.Experimental result shows, catalyst composition m (CaSO
4): m (CuSO
4): m (Na
2hPO
4): m (KH
2pO
4)=150.0:13.8:2.5:1.2,330 ℃ of temperature, lactic acid concn 26wt%, time of contact 88s, carrier gas CO
2, target product acrylic acid yield is up to 63.7%.Result of study also shows, catalyst can effectively be controlled its surface acidic strength through roasting, and carbon dioxide can to a certain degree suppress the generation of side reaction as carrier gas.The people such as Zhang [Ind.Eng.Chem.Res.2009,48,9083] adopt silicon dioxide carried phosphate catalysis methyl lactate Dehydration methyl acrylate and acrylic acid, and the activity of this catalyst series is evaluated.SiO is found in research
2/ NaH
2pO
4demonstrate and compare SiO
2/ Na
3pO
4or SiO
2/ Na
2hPO
4higher acrylate and acrylic acid overall selectivity, and NaH
2pO
4have best load capacity, high acid intensity and the density of P-OH of selectively thinking to change into phosphate transfection after catalyst roasting the poly-polyphosphoric acid end of the chain is relevant.Meanwhile, show Na in phosphate
2o and P
2o
5different quality proportioning also affect the catalytic performance of acid by dehydrating lactic.In addition, different N a/P impact on lactic acid conversion reaction than sodium ascorbyl phosphate catalyst series has also been studied by this group [Journal of Molecular Catalysis, 23,318,2009].The preparation of its catalyst is first by NaH
2pO
4with Na
2cO
3or H
3pO
4mix in varing proportions, then by infusion process, load on silica gel, finally by crossing roasting, make.Result of study shows Na/P ratio=1.2 o'clock, and phosphate catalyst surface acidic strength and sour density are suitable, and the reactivity of catalysis crylic acid preparation by lactic acid dehydration is best, and acrylic acid yield is up to 30%.It is because catalyst surface Quadrafos end POH has appropriate acidity that characterization result has disclosed high acrylic acid yield, and POH is the avtive spot of reaction.Lee etc. [Catal.Commun.2010,11,1176] have investigated the catalytic performance impact of the silica supports of different preparation methods' acquisitions on support type calcium phosphate.Silica supports makes by sol method, gel method, silicate precipitates method; Loaded catalyst makes by wet dipping or sol-gel process, active component Ca
3(PO
4)
2load capacity between 70%～95%.Wherein take sodium metasilicate as the prepared silica of the presoma precipitation method best.Best experimental result is, when catalyst forms wt (Ca
3(PO
4)
2): wt (SiO
2during)=80:20, catalytic effect is best, and rotational rate of lactic acid reaches 73.6%, and the overall selectivity of acrylic acid and methyl acrylate is 77.1%.Characterize comparative analysis and disclosed high selectivity owing to the suitable soda acid position distribution of catalyst surface.Peng Shaojun etc. [Beijing University of Chemical Technology's journal (natural science edition), 37,11,2010] be take silica gel as carrier, alkali metal dihydric phosphate MH
2pO
4(M=Li, Na, K) is active component, utilizes infusion process to prepare three kinds of load type polymerization phosphate catalyst M
2hPO
4/ SiO
2, on continuous flow reactor of fixed bed, investigated the reactivity worth impact of Different Alkali metal ion on methyl lactate Dehydration acrylic acid coproduction methyl acrylate.In three kinds of catalyst, Na
2hPO
4/ SiO
2the overall selectivity that catalysis methyl lactate generates acrylic acid and methyl acrylate is the highest, and when 380 ℃ of reaction temperatures, methyl lactate conversion ratio is 99.5%, and target product acrylic acid selectively can reach 52%.Catalyst characterization and quantum chemistry calculation show, alkali metal ion affects the acidity of the end P-OH of the acid density of catalyst surface and poly-microcosmic salt chain, and catalyst surface intermediate acid intensity and intermediate acid amount are conducive to improve product overall selectivity.Hong etc. [Applied Catalysis A:General 2011,396,194] have developed a kind of efficient, methyl lactate Dehydration acrylic acid of high selectivity and the complex salt catalyst of acrylate.This catalyst series is with Ca
3(PO
4)
2and Ca
2p
2o
7by different quality than making by pulpous state mixing method.Experimental result shows, the composite catalyst that proportioning is 50:50wt% has the highest activity and selectivity of product, and acrylic acid selection reaches 75%, and methyl acrylate is selectively 5%.Catalyst characterization analysis has disclosed high-temperature roasting and has given this catalyst surface suitable Acid-Base strengths, thereby this catalyst has higher catalytic perfomance.Silica gel load sodium nitrate be take as catalyst acid by dehydrating lactic under gas-solid phase reaction condition in Wadley etc. [Journal of Catalysis 1997,165,162] research group, finds that sodium lactate is a kind of active component.Active component sodium lactate is that lactic acid process is carried out proton translocation with sodium nitrate and forms, and the extra nitric acid generating of reaction evaporates with product.Experimental result shows: high temperature, low pressure, is conducive to acrylic acid generation short time of contact.[the Industrial & Engineering Chemistry Research 1993 such as Lira, 32,2608] near critical aqueous medium, use sodium hydrogen phosphate, phosphoric acid, and NaOH difference catalysis acid by dehydrating lactic, and be studied evaluation to generating three kinds of response paths of product acrylic acid, accessory substance acetaldehyde.During 360 ℃ of reaction temperatures, obtain best acrylic acid molar yield and reached 58%.Experimental result shows, adds a small amount of Na in lactic acid solution
2hPO
4can significantly improve acrylic acid molar yield, acrylic acid is selectively increased to 58% from 35%; Adding of NaOH makes acrylic acid molar yield maximum only have 45%; Reduce the adding of phosphoric acid acrylic acid selective.The application of first order reaction kinetics model has disclosed 0.04MNa
2hPO
4add and can improve the reaction rate constant that acrylic acid generates on a small quantity, but be more to have weakened such as decarboxylation, the generation of the side reactions such as decarbonylation.Recent Ghantani etc. [Green Chemistry 2013,15,1211] adopt hydroxyapatite catalysis crylic acid preparation by lactic acid dehydration, have obtained 60% yield.
Equations of The Second Kind: molecular sieve catalysts.As Y molecular sieve, NaY molecular sieve, ZSM-5 etc.Shi etc. [Chinese Chemical Letters 2007,18,476] have studied the catalytic effect of modified zeolite molecular sieve to methyl lactate dehydration generation methyl acrylate.Experiment finds, NaY type molecular sieve and KCl solution carry out ion-exchange etc. make KNaY molecular sieve than exchange before relatively, acid weakened, catalyst performance has improved, its experimental result acrylic acid molar yield 37.9% selectively reaches 45.7%.Wang etc. [Catalysis Communications 2008,9,1799] have investigated the NaY molecular sieve of rare earth metal modification for catalysis lactic acid acrylic acid processed, and associative list is gone on a punitive expedition opinion and analyzed the relation between catalyst structure and catalytic performance.Experimental result shows, wherein La
3+the NaY type molecular sieve of modifying has optimum catalytic performance, and La
3+having optimum load amount is 2wt%.In conjunction with characterization result, find La
3+introducing changed the surface nature of catalyst, as reduced surface acid density, expanded aperture and increased specific area etc.In addition, La
3+entering and having caused special structure cell distortion in NaY skeleton cage is to obtain the high optionally basic reason of acrylic acid.Profound, special distortion may affect absorption variation, reaction activity and the conversion pathway of lactic acid in reaction.Sun etc. [Catalysis Communications 2009,10,1345] have also carried out comparatively system research to NaY molecular sieve catalytic acid by dehydrating lactic.Experimental result shows, compares, through K with NaY type molecular sieve
+modification makes 2.8K/NaY type molecular sieve and not only greatly improves the selective of target product, the life-span of also having improved catalyst simultaneously.For example, acrylic acid selectively can bring up to 50% from 14.8%.Phenetic analysis shows, optimal catalyst has appropriate Acidity of Aikalinity and K
+the electronic effect raising of having given catalyst performance.[the Industrial & Engineering Chemistry Research 2010 such as Sun, 49,9082] the KNaY type molecular sieve catalytic producing acroleic acid by lactic acid dewatering that NaY molecular sieve makes by sylvite ion-exchange, high spot reviews the impact of sylvite anion on reactivity worth, and comparative analysis the experimental result of the molecular sieve modified front and back of NaY type, find modification after selectivity of product corresponding to NaY type molecular sieve all improve a lot.Wherein, with KI Modified K NaY type molecular sieve, have best catalytic performance, when 325 ℃ of reaction temperatures, rotational rate of lactic acid reaches 97.6%, and corresponding acrylic acid selectively reaches 67.9%.By Analysis on Mechanism, disclosed anion, by electronic effect, catalysis behavior applied to significant impact, macroscopic aspect be embodied in improved acrylic acid selective.Yan etc. [ChineseJournal of Catalysis 2011,32,405] have studied Ba
2+with La
3+the NaY molecular sieve catalytic producing acroleic acid by lactic acid dewatering of ion modification, has investigated the impact of the different preparation method of catalyst on catalyst pores structure and catalytic performance.Yu etc. [The Canadian Journal of Chemical Engineering 2011,89,484] have investigated with La
3+the NaY type molecular sieve of modifying, for catalysis acid by dehydrating lactic, utilizes series to characterize means analysis and has inquired into the impact of different catalyst preparation methods on its surface microporous structure and catalytic performance.Experiment is found, La
3+introducing can improve the catalytic performance of NaY molecular sieve.Meanwhile, compare original position synthetic, utilize the La/NaY molecular sieve that infusion process makes to show that high acrylic acid is selective, this is because different preparation methods has caused La
3+different in the residing position of molecular sieve, and position difference may affect Electric Field Distribution, reactant absorption situation, activation energy and response path etc.Yan etc. [Journal of Rare Earths 2010,28,803] have investigated through Ba
2+, La
3+with and K
+metal ion-modified NaY type molecular sieve catalytic lactic acid acrylic acid processed, and to reaction condition through having gone optimization.Experimental result surface, catalyst La/NaY molecular sieve has excellent catalyst performance, during 325 ℃ of reaction temperatures, obtains acrylic acid yield and reaches 56.3%.Contrast characterization result and show, the La/NaY catalyst surface of selectively giving the credit to that acrylic acid is high has suitable soda acid amount, suitably reduce the generation that sour amount and acid strength can weaken acetaldehyde, and raising alkali number and suitably reduction base strength is conducive to acrylic acid generation.Zhang etc. [ACS Catalysis 2011,1,32] have investigated the NaY molecular sieve catalytic lactic acid acrylic acid processed that alkali earth metal phosphate is modified, and from phosphatic type and load capacity, reaction temperature, liquid air speed and lactic acid concn aspect, reaction are optimized.Acquisition best result is: when lactic acid is at 340 ℃ of reaction temperatures, 14wt%Na
2hPO
4the acrylic acid yield making under/NaY catalyst action reaches 58.4%.Simultaneously, contrasted the sign spectrogram of catalyst before and after reaction, find that sodium phosphate has mainly changed into sodium lactate in reaction, the sodium lactate that original position produces is a kind of high activity component of catalysis goal response, and phosphatic introducing has reduced the acidity of catalyst surface.Holm etc. [Science 2010,328,602] have introduced take heterogeneous molecular sieve and prepares lactic acid derivative as catalyst carbohydrate transforms, as prepares methyl lactate.For example, when 160 ℃ of reaction temperatures, monose or polysaccharide are dissolved in methyl alcohol, Louis acid type molecular sieve is as its conversion of the catalysis such as Sn-Beta.Experimental result finds, take sucrose during as reaction substrate, and the yield of methyl lactate reaches 68%.Catalyst circulation is tested and is shown, heterogeneous molecular sieve can be reused after roasting, little on product selectivity impact.
The 3rd class solid heteropoly acid catalyst.The reaction of solid heteropoly acid catalysis acid by dehydrating lactic, is often accompanied by serious decarbonylation, decarboxylation side reaction, thereby is mainly used in decarbonylation, decarboxylic reaction.As [Green Chemistry 2010,12,1910.] such as Katryniok are used for the reaction of catalysis lactic acid decarbonylation acetaldehyde processed by heteropoly acid.Under gas solid catalytic reaction condition, SBA-15 is carrier, and silico-tungstic acid load capacity is 20wt%, and rotational rate of lactic acid reaches more than 91%, and selecting property of acetaldehyde reaches 83%, acrylic acid selectively extremely low.
In sum, the living beings lactic acid of take generally carries out as the acrylic acid production technology of raw material system under gas-solid phase reaction, between 300～450 ℃ of reaction temperatures, selects modified molecular screen to do the most study of catalyst.From result of study, rotational rate of lactic acid is generally higher, but acrylic acid is selectively generally lower, and the less stable of catalyst.Therefore, the emphasis of producing acroleic acid by lactic acid dewatering process route remains the catalyst of development efficient stable.
Summary of the invention
Patent of the present invention relates generally to sulfate catalysis crylic acid preparation by lactic acid dehydration, particularly alkali earth metal sulfate catalysis acid by dehydrating lactic.This catalyst stability is good, selectively high, low price, and preparation is simple, easy to utilize.
In one aspect of the invention, relate to a kind of catalyst of crylic acid preparation by lactic acid dehydration, it is characterized in that described catalyst prepares in the following way:
The alkaline-earth metal M salting liquid of employing solubility or alkali hydroxide earth metal M solution and dilute sulfuric acid or alkali metal sulfates solution reaction make alkali earth metal sulfate, and its amount of substance is than n (M
2+): n (SO
4 2-)=1:1, by prepared alkali earth metal sulfate sedimentation and filtration, and washs more than 3 times with distilled water, and with being placed on 110-130 ℃ of dry 4-6 hour in drying box, it is standby that dry end taking-up is placed in drier; Alkali earth metal sulfate is placed in Muffle furnace, adopts the calcining of temperature programming temperature control, and heating rate is 3-4 ℃/min, to design temperature, and calcining at constant temperature 3-7 hour; After it is cooling, utilize tablet press machine at 8-10MPa compressing tablet, broken, be screened to 40-50 order and obtain required catalyst; Described design temperature is 300～800 ℃, and preferably temperature is 450～600 ℃.
In a preferred embodiment of the present invention, described alkaline-earth metal M is selected from the combination of a kind of in calcium, magnesium, barium or two kinds, preferably barium and/or magnesium.
The present invention also relates to the application of above-mentioned catalyst in catalysis crylic acid preparation by lactic acid dehydration on the other hand.
In a preferred embodiment of the present invention, described application comprises the steps:
Choice of Quartz Tube Diameters, getting above-mentioned particle diameter is that 40～50 object Catalyst packings are central in quartz ampoule, uses silica wool end-blocking for two sections of catalyst; The above-mentioned quartz ampoule of having loaded catalyst is placed in to tube furnace, feeding line, carrier gas line and tail end sample collecting apparatus are connected; Feed pump adopts constant flow pump; Carrier gas adopts nitrogen; Sample divider adopts the gas-liquid separator with cold-trap.
In a preferred embodiment of the present invention, described reaction condition is that lactic acid input concentration is 10～50%, is preferably 15～25%; LHSV(liquid air speed) be 1～8h
-1, carrier gas is nitrogen, reaction temperature is 300～450 ℃.
In a preferred embodiment of the present invention, more than described catalyst successive reaction 7h.
In a preferred embodiment of the present invention, described rotational rate of lactic acid is 95-100%, and acrylic acid is selectively 60-70%, and the selective of acetaldehyde is 8-32%.
Accompanying drawing explanation
Fig. 1 CaSO
4the stability of catalyst: test condition: 400 ℃ of reaction temperatures, CaSO
40.5g, carrier gas N
21mL/min, feed rate 1mL/h, lactic acid concn: 20wt%.
Fig. 2 BaSO
4the stability experiment of catalyst: test condition: 400 ℃ of reaction temperatures, BaSO
40.5g, carrier gas N
21mL/min, feed rate 1mL/h, lactic acid concn: 20wt%.
The specific embodiment
Embodiment mono-
Take the BaSO of not roasting
40.8～1.2g, compressing tablet, grinding, get 20～40 object particles, is installed in the quartz ampoule that diameter is 3mm, with silica wool fixed catalyst BaSO
4, then the quartz ampoule that is filled with catalyst is placed in to heating furnace, open carrier gas (N
2) and pass into, open heater, in the mode of temperature programming (3～5 ℃/min), be that temperature reaches target temperature, steady temperature, passes into 20% lactic acid aqueous solution, collects product, for light yellow transparency liquid, analyze product, take gas chromatograph as testing tool, take n-butanol as interior mark, adopt FFAP capillary column, hydrogen flame (FID) detects, and the conversion ratio of testing result lactic acid is 99.5%, and acrylic acid is selectively 62%.
Embodiment bis-
Take the BaSO of roasting under 300 ℃ of conditions
40.8～1.2g, compressing tablet, grinding, get 20～40 object particles, is installed in the quartz ampoule that diameter is 3mm, with silica wool fixed catalyst BaSO
4, then the quartz ampoule that is filled with catalyst is placed in to heating furnace, open carrier gas (N
2) and pass into, open heater, in the mode of temperature programming (3～5 ℃/min), be that temperature reaches target temperature, steady temperature, passes into 20% lactic acid aqueous solution, collects product, for light yellow transparency liquid, analyze product, take gas chromatograph as testing tool, take n-butanol as interior mark, adopt FFAP capillary column, hydrogen flame (FID) detects, and the conversion ratio of testing result lactic acid is 99.5%, and acrylic acid is selectively 63%.
Embodiment tri-
Take the BaSO of roasting under 500 ℃ of conditions
40.8～1.2g, compressing tablet, grinding, get 20～40 object particles, is installed in the quartz ampoule that diameter is 3mm, with silica wool fixed catalyst BaSO
4, then the quartz ampoule that is filled with catalyst is placed in to heating furnace, open carrier gas (N
2) and pass into, open heater, in the mode of temperature programming (3～5 ℃/min), be that temperature reaches target temperature, steady temperature, passes into 20% lactic acid aqueous solution, collects product, for light yellow transparency liquid, analyze product, take gas chromatograph as testing tool, take n-butanol as interior mark, adopt FFAP capillary column, hydrogen flame (FID) detects, and the conversion ratio of testing result lactic acid is 99.5%, and acrylic acid is selectively 64.5%
Embodiment tetra-
Take the BaSO of roasting under 700 ℃ of conditions
40.8～1.2g, compressing tablet, grinding, get 20～40 object particles, is installed in the quartz ampoule that diameter is 3mm, with silica wool fixed catalyst BaSO
4, then the quartz ampoule that is filled with catalyst is placed in to heating furnace, open carrier gas (N
2) and pass into, open heater, in the mode of temperature programming (3～5 ℃/min), be that temperature reaches target temperature, steady temperature, passes into 20% lactic acid aqueous solution, collects product, for light yellow transparency liquid, analyze product, take gas chromatograph as testing tool, take n-butanol as interior mark, adopt FFAP capillary column, hydrogen flame (FID) detects, and the conversion ratio of testing result lactic acid is 99.5%, and acrylic acid is selectively 67%.
Embodiment five
Take the BaSO of roasting under 900 ℃ of conditions
40.8～1.2g, compressing tablet, grinding, get 20～40 object particles, is installed in the quartz ampoule that diameter is 3mm, with silica wool fixed catalyst BaSO
4, then the quartz ampoule that is filled with catalyst is placed in to heating furnace, open carrier gas (N
2) and pass into, open heater, in the mode of temperature programming (3～5 ℃/min), be that temperature reaches target temperature, steady temperature, passes into 20% lactic acid aqueous solution, collects product, for light yellow transparency liquid, analyze product, take gas chromatograph as testing tool, take n-butanol as interior mark, adopt FFAP capillary column, hydrogen flame (FID) detects, and the conversion ratio of testing result lactic acid is 99.5%, and acrylic acid is selectively 62.5%.
Embodiment six
Take the BaSO of roasting under 700 ℃ of conditions
40.8～1.2g, compressing tablet, grinding, get 20～40 object particles, is installed in the quartz ampoule that diameter is 3mm, with silica wool fixed catalyst BaSO
4, then the quartz ampoule that is filled with catalyst is placed in to heating furnace, open carrier gas (N
2) and pass into, open heater, in the mode of temperature programming (3～5 ℃/min), be that temperature reaches target temperature, steady temperature, passes into 10% lactic acid aqueous solution, collects product, for light yellow transparency liquid, analyze product, take gas chromatograph as testing tool, take n-butanol as interior mark, adopt FFAP capillary column, hydrogen flame (FID) detects, and the conversion ratio of testing result lactic acid is 99.5%, and acrylic acid is selectively 67%.
Embodiment seven
Take the BaSO of roasting under 700 ℃ of conditions
40.8～1.2g, compressing tablet, grinding, get 20～40 object particles, is installed in the quartz ampoule that diameter is 3mm, with silica wool fixed catalyst BaSO
4, then the quartz ampoule that is filled with catalyst is placed in to heating furnace, open carrier gas (N
2) and pass into, open heater, in the mode of temperature programming (3～5 ℃/min), be that temperature reaches target temperature, steady temperature, passes into 15% lactic acid aqueous solution, collects product, for light yellow transparency liquid, analyze product, take gas chromatograph as testing tool, take n-butanol as interior mark, adopt FFAP capillary column, hydrogen flame (FID) detects, and the conversion ratio of testing result lactic acid is 99.5%, and acrylic acid is selectively 67%.
Embodiment eight
Take the BaSO of roasting under 700 ℃ of conditions
40.8～1.2g, compressing tablet, grinding, get 20～40 object particles, is installed in the quartz ampoule that diameter is 3mm, with silica wool fixed catalyst BaSO
4, then the quartz ampoule that is filled with catalyst is placed in to heating furnace, open carrier gas (N
2) and pass into, open heater, in the mode of temperature programming (3～5 ℃/min), be that temperature reaches target temperature, steady temperature, passes into 30% lactic acid aqueous solution, collects product, for light yellow transparency liquid, analyze product, take gas chromatograph as testing tool, take n-butanol as interior mark, adopt FFAP capillary column, hydrogen flame (FID) detects, and the conversion ratio of testing result lactic acid is 99.5%, and acrylic acid is selectively 64%.
Embodiment nine
Take the MgSO of roasting under 500 ℃ of conditions
40.8～1.2g, compressing tablet, grinding, get 20～40 object particles, is installed in the quartz ampoule that diameter is 3mm, with silica wool fixed catalyst BaSO
4, then the quartz ampoule that is filled with catalyst is placed in to heating furnace, open carrier gas (N
2) and pass into, open heater, in the mode of temperature programming (3～5 ℃/min), be that temperature reaches target temperature, steady temperature, passes into 20% lactic acid aqueous solution, collects product, for light yellow transparency liquid, analyze product, take gas chromatograph as testing tool, take n-butanol as interior mark, adopt FFAP capillary column, hydrogen flame (FID) detects, and the conversion ratio of testing result lactic acid is 99.5%, and acrylic acid is selectively 63%.
Embodiment ten
Take the ZnSO of roasting under 500 ℃ of conditions
40.8～1.2g, compressing tablet, grinding, get 20～40 object particles, is installed in the quartz ampoule that diameter is 3mm, with silica wool fixed catalyst BaSO
4, then the quartz ampoule that is filled with catalyst is placed in to heating furnace, open carrier gas (N
2) and pass into, open heater, in the mode of temperature programming (3～5 ℃/min), be that temperature reaches target temperature, steady temperature, passes into 20% lactic acid aqueous solution, collects product, for light yellow transparency liquid, analyze product, take gas chromatograph as testing tool, take n-butanol as interior mark, adopt FFAP capillary column, hydrogen flame (FID) detects, and the conversion ratio of testing result lactic acid is 50%, and acrylic acid is selectively 25%.
Embodiment 11
Take the NiSO of roasting under 500 ℃ of conditions
40.8～1.2g, compressing tablet, grinding, get 20～40 object particles, is installed in the quartz ampoule that diameter is 3mm, with silica wool fixed catalyst BaSO
4, then the quartz ampoule that is filled with catalyst is placed in to heating furnace, open carrier gas (N
2) and pass into, open heater, in the mode of temperature programming (3～5 ℃/min), be that temperature reaches target temperature, steady temperature, passes into 20% lactic acid aqueous solution, collects product, for light yellow transparency liquid, analyze product, take gas chromatograph as testing tool, take n-butanol as interior mark, adopt FFAP capillary column, hydrogen flame (FID) detects, and the conversion ratio of testing result lactic acid is 99.5%, and acrylic acid is selectively 30%.
Comparative study the stability of barium sulfate catalyst and calcium sulfate catalyst, barium sulfate catalyst stability is better than calcium sulfate catalyst.For example barium sulfate catalyst moves 80h continuously, and rotational rate of lactic acid is down to 90% by 100%, acrylic acidly selectively by 76%, is down to 50%; And calcium sulfate catalyst moves 5h continuously, rotational rate of lactic acid is down to 75%.Experimental result is as Fig. 1, shown in 2.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, do not departing under the prerequisite of principle of the present invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (8)
1. a catalyst for crylic acid preparation by lactic acid dehydration, is characterized in that described catalyst prepares in the following way:
The alkaline-earth metal M salting liquid of employing solubility or alkali hydroxide earth metal M solution and dilute sulfuric acid or alkali metal sulfates solution reaction make alkali earth metal sulfate, and its amount of substance is than n (M
2+): n (SO
4 2-)=1:1, by prepared alkali earth metal sulfate sedimentation and filtration, and washs more than 3 times with distilled water, and with being placed on 110-130 ℃ of dry 4-6 hour in drying box, it is standby that dry end taking-up is placed in drier; Alkali earth metal sulfate is placed in Muffle furnace, adopts the calcining of temperature programming temperature control, and heating rate is 3-4 ℃/min, to design temperature, and calcining at constant temperature 3-7 hour; After it is cooling, utilize tablet press machine at 8-10MPa compressing tablet, broken, be screened to 40-50 order and obtain required catalyst; Described design temperature is 300～800 ℃, and preferably temperature is 450～600 ℃.
2. the catalyst of crylic acid preparation by lactic acid dehydration according to claim 1, is characterized in that the alkali salt of described solubility or alkaline-earth metal aqueous slkali are selected from calcium chloride, limewash, calcium nitrate; Barium chloride, barium hydroxide, barium nitrate; Strontium nitrate, strontium chloride etc.; The alkali metal sulfates of solubility is selected from sodium sulphate, potassium sulfate, and dilute sulfuric acid comes as for spent acid more.
3. the catalyst of crylic acid preparation by lactic acid dehydration according to claim 1, described alkaline-earth metal M is selected from the combination of a kind of in calcium, magnesium, barium or two kinds, preferably barium and/or magnesium.
4. the application of the catalyst described in claim 1-3 any one in catalysis crylic acid preparation by lactic acid dehydration.
5. application according to claim 4, described application comprises the steps:
Choice of Quartz Tube Diameters, getting above-mentioned particle diameter is that 40～50 object Catalyst packings are central in quartz ampoule, uses silica wool end-blocking for two sections of catalyst; The above-mentioned quartz ampoule of having loaded catalyst is placed in to tube furnace, feeding line, carrier gas line and tail end sample collecting apparatus are connected; Feed pump adopts constant flow pump; Carrier gas adopts nitrogen; Sample divider adopts the gas-liquid separator with cold-trap.
6. application according to claim 5, described reaction condition is that lactic acid input concentration is 10～50%, is preferably 15～25%; LHSV(liquid air speed) be 1～8h
-1, carrier gas is nitrogen, reaction temperature is 300～450 ℃.
7. application according to claim 5, more than described catalyst successive reaction 7h.
8. according to the application described in claim 5 or 6, described rotational rate of lactic acid is 95-100%, and acrylic acid is selectively 60-70%, and the selective of acetaldehyde is 8-32%.
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| CN108993479A (en) * | 2018-08-07 | 2018-12-14 | 重庆理工大学 | Catalyst with base of molybdenum, preparation method and applications |
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| CN108993479A (en) * | 2018-08-07 | 2018-12-14 | 重庆理工大学 | Catalyst with base of molybdenum, preparation method and applications |
| CN112479262A (en) * | 2020-11-27 | 2021-03-12 | 重庆理工大学 | Method for preparing iron oxide and preparing pyruvic acid by catalyzing lactic acid |
| CN112479262B (en) * | 2020-11-27 | 2023-09-26 | 重庆理工大学 | Method for preparing ferric oxide and preparing pyruvic acid by catalyzing lactic acid |
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