CN110105190A - Method for producing acrylic acid based on lactic acid aqueous solution of ester - Google Patents
Method for producing acrylic acid based on lactic acid aqueous solution of ester Download PDFInfo
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- CN110105190A CN110105190A CN201810101753.XA CN201810101753A CN110105190A CN 110105190 A CN110105190 A CN 110105190A CN 201810101753 A CN201810101753 A CN 201810101753A CN 110105190 A CN110105190 A CN 110105190A
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- acrylic acid
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- aqueous solution
- ester
- lactic acid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7007—Zeolite Beta
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7038—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7042—TON-type, e.g. Theta-1, ISI-1, KZ-2, NU-10 or ZSM-22
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
Abstract
The present invention provides a kind of method for producing acrylic acid based on lactic acid aqueous solution of ester, using lactic acid aqueous solution of ester as raw material, under the action of zeolite catalyst and/or hydroxyapatite catalyst, makes the lactate that the reaction of gas phase selectively dewatering occur and generates acrylic acid.
Description
Technical field
The present invention relates to biomass resource catalyzed conversions to utilize technical field, water-soluble based on lactate more particularly to one kind
The method for producing acrylic acid of liquid.
Background technique
Acrylic acid is a kind of important Organic Chemicals and polymer monomer, (is accounted for about mainly for the production of acrylate
55%) and super water absorbent resin (accounting for about 32%), there are huge market demand (about 6,000,000 tons).Industrial main use
Propylene (or propane) catalysis oxidation based on non-renewable petroleum produces acrylic acid, is realized using biomass derivatives lactic acid
One of the technological approaches of acrylic acid production sustainable development.But current lactic acid is on the high side, while the acidity of lactic acid is stronger
(pKa=3.85), strong to consersion unit corrosivity, high production cost.Compared with conventional petroleum base route, using biomass-based cream
The route that acrylic acid is produced in acid dehydration wouldn't have economic feasibility.Currently, being badly in need of a kind of economically viable acrylic acid preparation side
Method.
Summary of the invention
Based on this, it is necessary to for production of lactic acid acrylic acid problem at high cost, provide a kind of based on lactic acid aqueous solution of ester
Method for producing acrylic acid.
A kind of method for producing acrylic acid based on lactic acid aqueous solution of ester is urged using lactic acid aqueous solution of ester as raw material in zeolite
Under the action of agent and/or hydroxyapatite catalyst, makes the lactate that the reaction of gas phase selectively dewatering occur and generate propylene
Acid.
In one of the embodiments, the lactic acid aqueous solution of ester be methyl lactate aqueous solution, ethyl lactate aqueous solution or
The mixing of the two.
In one of the embodiments, the partial pressure of lactate described in gas phase selectively dewatering reaction be 10kPa with
Under, the partial pressure of water is 10~50kPa.
It in one of the embodiments, include metal cation in the zeolite catalyst, the metal cation includes
One or more of alkali metal ion, alkaline-earth metal ions and rare earth ion.
The alkali metal ion includes Li in one of the embodiments,+、Na+、K+、Rb+、Cs+One of or it is a variety of,
The alkaline-earth metal ions include Mg2+、Ca2+、Sr2+、Ba2+One of or it is a variety of, the rare earth ion includes La3+、
Ce4+One of or it is a variety of.
The metal cation in the zeolite catalyst is two kinds in one of the embodiments, described two gold
Belonging to cation is Na+And K+、Na+And Rb+Or Na+And Cs+。
The metal cation in the zeolite catalyst is K in one of the embodiments,+And Na+, the K+With
Na+Molar ratio be 50/50~100/0.
The zeolite catalyst includes ZSM-5, β, MCM-22, MOR, ZSM-22, ZSM-35 in one of the embodiments,
One or more of with X-type zeolite.
In one of the embodiments, in the zeolite catalyst total electrical charge number of metal cation and aluminium atom number ratio
Value >=0.8.
SiO in zeolite skeleton in the zeolite catalyst in one of the embodiments,2/A12O3Molar ratio be 15~
40。
The volume space velocity (GHSV) in the gas phase selectively dewatering reaction is 1000h in one of the embodiments,-1~
9000h-1, reaction temperature is 300~400 DEG C.
The hydroxyapatite catalyst Formula is M in one of the embodiments,10(XO4)6Y2, wherein M is divalent sun
Ion Ca2+、Sr2+、Pb2+One of or it is a variety of；XO4For PO4 3-、VO4 3-One of or it is a variety of；Y is OH-、F-It is middle a kind of or
It is a variety of.
The hydroxyapatite catalyst is calcium hydroxy phosphate in one of the embodiments, the calcium hydroxy phosphate
Ca/P molar ratio is≤1.67, maturing temperature≤700 DEG C in the preparation process of the hydroxyapatite catalyst.
In the above-mentioned method for producing acrylic acid based on lactic acid aqueous solution of ester, by the effect of catalyst, so that lactate
Aqueous solution is converted to acrylic acid, and not only cost of material is low, but also lactate is small to the corrosion of equipment, and equipment cost is lower.Therefore
Researching value and application prospect are had more using the synthetic route that acrylic acid is produced in the selective catalysis dehydration of lactic acid aqueous solution of ester, made
It acrylic acid industrialization large-scale production and low in cost is possibly realized.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, by embodiment, the present invention is implemented
The method for producing acrylic acid based on lactic acid aqueous solution of ester of example is further elaborated.It should be appreciated that described herein
Specific examples are only used to explain the present invention, is not intended to limit the present invention.
A kind of method for producing acrylic acid based on lactic acid aqueous solution of ester is urged using lactic acid aqueous solution of ester as raw material in zeolite
Under the action of agent and/or hydroxyapatite catalyst, makes lactate that the reaction of gas phase selectively dewatering occur and generate acrylic acid.
In the lactic acid aqueous solution of ester, the concentration of lactate is preferably 5~90wt%, further preferably 50wt% with
Under.Lactate is preferably methyl lactate and/or ethyl lactate, and the methyl lactate and/or the ethyl lactate are as reaction
Raw material, not only cost of material is low, but also the methyl lactate and the ethyl lactate are small to the corrosivity of equipment, and equipment cost is more
It is low.The methyl lactate or the ethyl lactate can be raw material by the by-product glycerin of biodiesel, be molten with low-carbon alcohols
The catalytic oxidation process of agent is made.Oneself is improved several times in the production technology of biodiesel is gone over 10 years, and glycerol is as biology
A kind of by-product of diesel oil industry can be obtained largely, and the lactate can largely be obtained by glycerol.
Gas phase selectively dewatering reaction, it is preferred the following steps are included:
The lactic acid aqueous solution of ester is input in the reactor for being filled with the catalyst with sampling pump, and is carried with inertia
Gas phase is preheated to after gas mixing；And
So that the raw material containing lactate is contacted generation dehydration with the catalyst and obtains acrylic acid.The reactor can
Think the reactors such as fixed bed reactors, fluidized-bed reactor, moving-burden bed reactor.The inert gas can be nitrogen, two
Carbon oxide gas, vapor, air etc..Reaction feed technique preferably heats lactate, it is made at least to reach catalyst bed
Gaseous state has been in when layer.
The lactate is mixed with inert carrier gas, is the partial pressure in order to adjust lactate described in unstripped gas and water, described
The partial pressure of lactate refers to lactate pressure/(lactate pressure+water pressure+inert carrier gas pressure), the partial pressure of the lactate
Preferably 20kPa is hereinafter, further preferably 10kPa or less, it is preferred that control the lactate partial pressure be 3.9kPa with
Under, the partial pressure of the particularly preferred lactate is 3kPa or less；The partial pressure of water is preferably 5~85kPa, further preferably 10~
50kPa, particularly preferably 15~35kPa.
In the gas phase selectively dewatering reaction, the flow of unstripped gas, to be handled in unit time per volume of catalyst
The volume (i.e. volume space velocity: GHSV) of unstripped gas indicates that the volume space velocity (GHSV) is preferably 10000h-1Hereinafter, being, for example,
1000h-1~9000h-1, further preferably 5000h-1Hereinafter, particularly preferably 2000h-1Below.The gas phase is selectively de-
Water reaction temperature refers to that the set temperature of thermophore controlled the temperature of reactor etc., reaction temperature of the invention are preferred
It is 250~500 DEG C, further preferably 300~400 DEG C, particularly preferably 350~380 DEG C.For the gas phase of the lactate
Selectively dewatering reaction, too low or excessively high reaction temperature can reduce the yield of acrylic acid.
The gas phase selectively dewatering reaction generates acrylic acid solution, and further preferred further includes obtaining reaction
Acrylic acid is recycled in a manner of acrylic acid solution condensation or solvent trapping etc..It can also trap and contain including the use of liquid medium
The trapping separation process of the gas of acrylic acid or condensation and the condensation and separation process for trapping gas containing acrylic acid.By adopting
For example distill with previous traditional method, rectifying or crystallization etc. refine acrylic acid solution, the acrylic acid of high-purity can be obtained.
The catalyst includes zeolite catalyst, and the zeolite catalyst includes metal cation, the metal cation
Play the role of balance skeleton negative electrical charge.Although the present invention is to the type of metal cation in the zeolite catalyst without special
It limits, it is preferred that containing alkali metal ion (Li+、Na+、K+、Rb+、Cs+), alkaline-earth metal ions (Mg2+、Ca2+、Sr2+、Ba2+)
With rare earth ion (La3+、Ce4+At least one of Deng), further preferably one of alkali metal ion or more
Kind.
Preferably, the zeolite catalyst of the invention preferably is selected from least two in alkali metal ion and alkaline-earth metal ions
Kind metal cation is as the metal cation for balancing its skeleton negative electrical charge.Use such zeolite as by lactate preparation third
When the catalyst of olefin(e) acid, high acrylic acid yield can get.More preferably contain the zeolite of two or more alkali metal ions
Catalyst.Consider from the easy preparative of catalyst and preparation cost etc., preferably Li+、Na+、K+、Ca2+And Mg2+In
At least two metal cations as alkali metal ion and alkaline-earth metal ions.
Further from the aspect of catalyst performance, the cation in zeolite of the invention is more preferably Na+And K+。
Further, zeolite of the invention contains Na+And K+In the case where, K+And Na+Ratio do not limit particularly
It is fixed, but K+And Na+Molar ratio be preferably greater than 50/50, more preferably 80/20 or more, particularly preferably 90/10 or more.It is another
Aspect, as K+And Na+Molar ratio the upper limit, preferred molar ratio be 98/2 or less.
The catalyst, the molar content ratio of cationic total electrical charge number and aluminium atom in the preferred zeolite catalyst
Value is >=0.80.It is further preferred that the total electrical charge number of metal cation and aluminium atom molar content in the zeolite catalyst
Ratio be >=0.90.
Alkali metal in the zeolite catalyst be in the form of balance cation existing for.M represents the gold for replacing Na ion
Belong to ion, x indicates that ion-exchange degree, y indicate SiO in zeolite skeleton2With Al2O3Molar ratio.According to the type of alkali metal ion
(K+、Rb+Or Cs+), ion-exchange degree (x=[M]/([M]+[Na]), SiO2With Al2O3Molar ratio (y) by resulting catalyst
It is indicated with MxNa1-xW_y, W is the type of zeolite catalyst skeleton, and wherein the value of x and y is by X-ray fluorescence spectrometer
XRF is measured.The type of the skeleton of the zeolite catalyst, it is preferred that can be ZSM-5, β, MCM-22, MOR, ZSM-22,
ZSM-35 or X-type zeolite.Such as the skeleton of the zeolite catalyst is ZSM-5, is indicated with MxNa1-xZSM-5_y.
The zeolite catalyst, it is preferred that the SiO of the zeolite catalyst2With Al2O3Molar ratio is 15 to 40.It is preferred that
, the zeolite catalyst SiO2With Al2O3Molar ratio be 18 to 30.
It is further preferred that the zeolite catalyst is preferably K0.95Na0.05ZSM-5_27.The K0.95Na0.05ZSM-5_
SiO in 27 zeolite skeletons2With Al2O3Molar ratio be 27, with Na+And K+For the metal cation of balance skeleton negative electrical charge.
ZSM-5, β, MCM-22, MOR, ZSM-22, ZSM-35 or X-type zeolite and hydroxyapatite according to the present invention can
To be commercial product or commercially available product, can also be prepared by conventional method.But the preferred root of the zeolite catalyst of the invention
It is prepared according to needing to carry out cation exchange.
Preferably, the zeolite catalyst preparation method the following steps are included:
S10, by commodity or pass through ZSM-5, β, MCM-22, MOR, ZSM-22, ZSM-35 or X-type etc. prepared by conventional method
Zeolite powder is placed in Muffle furnace, is roasted 1~12 hour under static or moving air in 400~650 DEG C, is removed in zeolite
Template is obtained with H+Or Na+For the zeolite of balance skeleton negative electrical charge cation, it is denoted as HZ or NaZ.
S11, above-mentioned HZ or NaZ zeolite is added in the solution containing cation A, is then heated, is stirred, Ji Kefa
Raw cation exchange reaction, obtains the zeolite using A as balance cation.
It is further preferred that by being added in the solution containing cation B using A as the zeolite of balance cation, continuation and B
It swaps, can be obtained simultaneously containing two kinds of cationic zeolites of A and B.
The degree of cation exchange, can by the concentration, the temperature of exchange reaction of metal target cation in solution and
The operating parameters such as time and exchange times are adjusted.If the operation by primary ions exchange reaction cannot reach institute
Desired cation exchange degree, the then preferred number of operations for increasing ion-exchange reactions, by by the behaviour of ion-exchange reactions
It is repeated as many times, cationic exchange degree is made to be increased to desired degree.
S12, the zeolite exchanged by above-mentioned cation, can according to need implementation drying and/or calcination process.For example, roasting
Burning processing can be heated to 400~650 DEG C of 1~12h of holding under air atmosphere, sample.
When the catalyst is hydroxyapatite, the hydroxyapatite catalyst Formula is M10(XO4)6Y2, wherein M
For bivalent cation Ca2+、Sr2+、Pb2+Deng one of or it is a variety of；XO4For PO4 3-、VO4 3-Deng one of or it is a variety of；Y is
OH-、F-In it is one or more.Hydroxyapatite of the present invention can be commercial product or commercially available product, can also be by traditional
Method preparation.Preferably, it is prepared by the precipitation method.
Catalyst hydroxyapatite (the M10(XO4)6Y2) preparation method, comprising the following steps:
S20, Xiang Hanyou M2+And XO4 3-The aqueous slkalis such as ammonium hydroxide, NaOH or KOH are added in solution；
S21, it continuously stirs, the pH for adjusting solution is 7~12；
S22, the obtained precipitating of reaction through standing aging, be filtered, washed and etc. obtain the hydroxyapatite.
From the aspect of the catalytic performance obtained, it is preferred that further include step S23, be catalyzed to the hydroxyapatite
Agent is roasted.Need to carry out the hydroxyapatite calcination process, preferred maturing temperature is 700 DEG C hereinafter, further
Preferably, maturing temperature≤500 DEG C of the hydroxyapatite catalyst, still more preferably, the hydroxyapatite is urged
Maturing temperature≤400 DEG C of agent.
Preferably, the hydroxyapatite catalyst is calcium hydroxy phosphate.
Such as when preparing calcium hydroxy phosphate, optional calcium source, such as calcium nitrate, calcium chloride, calcium hydroxide, optional phosphorus
Source, such as soluble phosphate, it is preferred that phosphoric acid ammonia and phosphoric acid hydrogen ammonia.
The calcium hydroxy phosphate has very strong ion-exchange performance, the Ca in crystal structure2+、PO4 3-And OH-It can be with
Other ions exchange, to make Ca2+And PO4 3-Molar ratio (i.e. Ca/P ratio) change.
The pH of solution obtains the hydroxyl of different Ca/P ratios when the ratio and reaction of the calcium source and phosphorus source that are added by adjusting
Calcium phosphate.Heating temperature range when synthesis is 0~100 DEG C, and mixing time is 1~12h.The prepared hydroxyapatite
It can according to need implementation drying or calcination process.Sample under air environment can be heated to 300 by the calcination process~
800 DEG C of 1~12h of holding.
The calcium hydroxy phosphate of the invention is to contained Ca2+And PO4 3-Molar ratio there is no particular limitation.Preferably,
The calcium hydroxy phosphate Ca/P molar ratio is≤1.67.It is further preferred that the Ca/P molar ratio of the calcium hydroxy phosphate is preferred
It is≤1.63.Still more preferably, the Ca/P molar ratio of the calcium hydroxy phosphate is≤1.60.
Catalyst of the invention, in addition to zeolites such as described ZSM-5, β, MCM-22, MOR, ZSM-22, ZSM-35 or X-types or
Other than the hydroxyapatite, other ingredients can also be contained.For example, it is also possible to be the zeolite being supported on specific support
Or the hydroxyapatite, i.e. support type zeolite or hydroxyapatite catalyst.Wherein carrier material can be silica, oxygen
Change inorganic oxides or the composite oxides such as aluminium, titanium dioxide, zirconium oxide, containing other crystallinity such as heteroatomic zeolite molecular sieves
Silicate, inorganic matters such as active carbon, silicon carbide etc., the metal or alloy such as stainless steel, aluminium.
Catalyst of the invention can also be unsupported catalyst.For example, adhesive can be added in zeolite and made
It can also be made ands the silica supports of specific shape are transformed to zeolite etc. at the preformed catalyst of various statuses
The full zeolite catalyst for being free of adhesive.
The present invention can be spherical, granular, column, ring-type, saddle, honeycomb, powdered etc. to the shape of catalyst.
The institute of the zeolite containing metal cation or di apatite of the invention can be prepared by above method
State catalyst.It these described catalyst are used to the lactate dehydration can be improved prepare the conversion ratio of the acrylic acid
And selectivity.
Embodiment 1
[catalyst preparation]
By SiO2/Al2O3Molar ratio is 27, with sodium ion (Na+) boiled for the ZSM-5 type of balance skeleton negative electrical charge cation
Stone powder, which is placed in Muffle furnace to roast 5 hours in 500 DEG C, obtains NaZSM-5_27.NaZSM-5_27 after weighing 3g roasting impregnates
In the KBr aqueous solution that 60ml concentration is 0.1mol/L, 1 hour progress ion-exchange reactions is stirred at 80 DEG C, using pumping
Filter, drying, finally roast 3 hours at 500 DEG C, obtain the first with Na+It is the ZSM-5 of balance skeleton negative electrical charge cation with K+
Zeolite catalyst, the catalyst are denoted as K0.95Na0.05ZSM-5_27。
[acrylic acid preparation]
The gas phase selectively dewatering reaction of ethyl lactate aqueous solution is under normal pressure, continuously to flow quartz fixed bed reactor
It is carried out on (long: ca.50cm, internal diameter: ca.9mm).
Specific step is as follows: taking the K of 500mg0.95Na0.05ZSM-5_27 catalyst (20~40 mesh) is seated in reaction tube
Portion is clipped among two layers of quartz wool, and the top reloading about 2ml quartz sand (20~40 mesh) of upper layer quartz wool is used for pre- thermal response
Raw material.React procatalyst (360 DEG C), 25ml min at the reaction temperatures-1Drying N2Middle purging 1.5h；Micro-injection is used again
The ethyl lactate aqueous solution that molar concentration is 5% is injected into reactor by pump with the speed of 0.9ml/h, at this time the group of unstripped gas
Partial pressure as ethyl lactate is 1.8kPa, the partial pressure of water partial pressure 35.1kPa, nitrogen is 63.1kPa.Reaction product is placed in ice
The condenser pipe of (0 DEG C) is collected in water-bath, and a sample is taken to be analyzed per hour.
Measurement result based on gas-chromatography, according to following calculating formulas, calculate lactate conversion ratio (EL conversion ratio),
Acrylic acid selectivity (AA selectivity), acrylic acid yield (AA yield).
EL conversion ratio (%)=(molal quantity of the lactate consumed in reaction)/(is input to the lactate of reactor
Molal quantity) × 100%.
AA selectivity (%)=(molal quantity of the carbon atom in acrylic acid generated in reaction)/(consumes in reaction
The molal quantity of carbon atom in lactic acid) × 100%.
AA yield (%)=EL conversion ratio × selectivity × 100 AA.
Influence of table 1a, the embodiment 1 different reaction time to conversion ratio
| Reaction time (h) | Reaction raw materials | Lactate divides (kPa) | Water partial pressure (kPa) |
| 10 | Ethyl lactate | 1.8 | 35.1 |
| 50 | Ethyl lactate | 1.8 | 35.1 |
| 100 | Ethyl lactate | 1.8 | 35.1 |
| 150 | Ethyl lactate | 1.8 | 35.1 |
| 200 | Ethyl lactate | 1.8 | 35.1 |
| 250 | Ethyl lactate | 1.8 | 35.1 |
Influence of the embodiment 1b different reaction time to conversion ratio
Influence of the different reaction time of embodiment 1 to conversion ratio is shown in Table 1a and table 1b, the K0.95Na0.05ZSM-5_27
50h declines very fast (ca.7%) conversion ratio of ethyl lactate before the reaction on catalyst, and the conversion of 50~250h ethyl lactate
Rate only has dropped less than 5%, and still is able to maintain 80% or more, shows good stability；And during the reaction
The selectivity of target product is able to maintain that 90% or more.
Influence of the different reaction temperature of table 1c, embodiment 1 to conversion ratio
Influence of the different reaction volume air speed of table 1d, embodiment 1 to conversion ratio
Different reaction temperatures and different volume space velocities the results are shown in Table 1c and table 1d, pass through the K0.95Na0.05ZSM-
5_27 catalyst, when reaction temperature is 340 DEG C, 350 DEG C, 360 DEG C, 370 DEG C, the selectivity of acrylic acid is both greater than 60%, all table
Reveal highly selective, volume space velocity 2460h-1、3690h-1、4920h-1、6150h-1When, the selectivity of acrylic acid is both greater than
60%.
Embodiment 2
[catalyst preparation]
The preparation method of catalyst is same as Example 1.
[acrylic acid preparation]
Reaction raw materials are that the molar concentration of methyl lactate aqueous solution is 5%, other reaction conditions are same as Example 1.It is real
Applying influence of the different reaction time of example 2 to conversion ratio the results are shown in Table 2a and table 2b.
Influence of the embodiment 2a different reaction time to conversion ratio
| Reaction time (h) | Reaction raw materials | Lactate divides (kPa) | Water partial pressure (kPa) |
| 10 | Methyl lactate | 1.8 | 35.1 |
| 50 | Methyl lactate | 1.8 | 35.1 |
| 100 | Methyl lactate | 1.8 | 35.1 |
| 150 | Methyl lactate | 1.8 | 35.1 |
| 200 | Methyl lactate | 1.8 | 35.1 |
| 250 | Methyl lactate | 1.8 | 35.1 |
Influence of the embodiment 2b different reaction time to conversion ratio
K0.95Na0.05On ZSM-5_27 catalyst methyl lactate gas-phase dehydration reaction equally show good stability and
The selectivity (85% or more) of target product.
Embodiment 3
[catalyst preparation]
The preparation method of catalyst is same as Example 1.
[acrylic acid preparation]
Reaction raw materials are changed to 10mol% ethyl lactate aqueous solution by 5mol% ethyl lactate aqueous solution, sample volume is
1.2ml/h, and by adjusting N2Flow keep the partial pressure of total air speed and water constant, at this time the group of unstripped gas become 3.9kPa cream
Acetoacetic ester, water partial pressure 35.1kPa, nitrogen partial pressure 61.0kPa.Other reaction conditions are same as Example 1, and gained reaction result is shown in
Table 3a and table 3b.
Embodiment 4
[catalyst preparation]
The preparation method of catalyst is same as Example 1.
[acrylic acid preparation]
Reaction raw materials are changed to 20mol% ethyl lactate aqueous solution by 5mol% ethyl lactate aqueous solution, sample volume is
1.8ml/h, and by adjusting N2Flow keep the partial pressure of total air speed and water constant, at this time the group of unstripped gas become 8.8kPa cream
Acetoacetic ester, water partial pressure 35.1kPa, nitrogen partial pressure 56.1kPa.Other reaction conditions are same as Example 1, gained reaction result
See, gained reaction result is shown in Table 3a and table 3b.
Embodiment 5
[catalyst preparation]
The preparation method of catalyst is same as Example 1.
[acrylic acid preparation]
Reaction raw materials are changed to pure ethyl lactate by 10mol% ethyl lactate aqueous solution, sample volume 0.5ml/h, and
By adjusting N2Flow keep total air speed constant, at this time the group of unstripped gas become 3.9kPa ethyl lactate/0kPa water/
96.1kPa N2.Other reaction conditions are same as Example 3, and gained reaction result is shown in Table table 3a and table 3b.
Embodiment 6
[catalyst preparation]
The preparation method of catalyst is same as Example 1.
[acrylic acid preparation]
Reaction raw materials are changed to 4.5mol% ethyl lactate aqueous solution by 10mol% ethyl lactate aqueous solution, sample volume is
2.2ml/h, and by adjusting N2Flow keep total air speed constant, the group of unstripped gas becomes 3.9kPa ethyl lactate and divides at this time
Pressure, water partial pressure 84.0kPa, nitrogen partial pressure 12.1kPa.Other reaction conditions gained reaction result same as Example 3 is shown in
Table 3a and table 3b.
The influence of table 3a, different partial pressures to conversion ratio
The influence of table 3b, different partial pressures to conversion ratio
No matter comparing embodiment 1,2,3,4,5,6 is it is found that the partial pressure of ethyl lactate or the partial pressure of water can all significantly affect
K0.95Na0.05The performance of the gas-phase dehydration reaction of ethyl lactate on ZSM-5_27 catalyst.According to data it is found that the lactate
Partial pressure in 10kPa hereinafter, the selectivity of its acrylic acid can achieve 78% or more, when the partial pressure of the lactate is 3.9kPa
When following, the selectivity of acrylic acid can achieve 80% or more, and lactic acid ester conversion rate can achieve 58% or more.The lactate
Partial pressure be preferably 3.9kPa or less；The partial pressure of water is preferably 5~85kPa or more.Embodiment 1, when water partial pressure is 35.1kPa
When, the lactate partial pressure (kPa) is 1.8, the water partial pressure (kPa) 35.1, and lactic acid ester conversion rate is 94%, acrylic acid choosing
Selecting property is to 86%.
Embodiment 7
[catalyst preparation]
By SiO in embodiment 12/Al2O3Than being changed to SiO for 27 NaZSM-52/Al2O3Than the NaZSM-5 for 13, other
Preparation condition is same as Example 1, and the catalyst being prepared is denoted as K0.95Na0.05ZSM-5_13。
[acrylic acid preparation]
Reaction condition is same as Example 3, and gained reaction result is shown in Table 4.
Embodiment 8
[catalyst preparation]
By SiO in embodiment 12/Al2O3Than being changed to SiO for 27 NaZSM-52/Al2O3Than the NaZSM-5 for 18, other
Preparation condition is same as Example 1, and the catalyst being prepared is denoted as K0.95Na0.05ZSM-5_18。
[acrylic acid preparation]
Reaction condition is same as Example 3, and gained reaction result is shown in Table 4.
Embodiment 9
[catalyst preparation]
Preparation condition is same as Example 1, and the catalyst being prepared is denoted as K0.95Na0.05ZSM-5_27。
[acrylic acid preparation]
Reaction condition is same as Example 3, and gained reaction result is shown in Table 4.
Embodiment 10
[catalyst preparation]
By SiO in embodiment 12/Al2O3Than being changed to SiO for 27 NaZSM-52/Al2O3Than the NaZSM-5 for 48, other
Preparation condition is same as Example 1, and the catalyst being prepared is denoted as K0.95Na0.05ZSM-5_48。
[acrylic acid preparation]
Reaction condition is same as Example 3, and gained reaction result is shown in Table 4.
Embodiment 11
[catalyst preparation]
By SiO in embodiment 12/Al2O3Than being changed to SiO for 27 NaZSM-52/Al2O3Than the NaZSM-5 for 75, other
Preparation condition is same as Example 1, and the catalyst being prepared is denoted as K0.95Na0.05ZSM-5_75。
[acrylic acid preparation]
Reaction condition is same as Example 3, and gained reaction result is shown in Table 4.
Table 4, difference SiO2/Al2O3Compare the influence of conversion ratio
As shown in table 4, the SiO of the zeolite catalyst2With Al2O3Molar ratio be 13 when, the conversion of the acrylic acid
Rate is 34%, acrylic acid selectivity 61%；The SiO of the zeolite catalyst2/Al2O3Molar ratio be 18 when, described third
The conversion ratio of olefin(e) acid is 53%, acrylic acid selectivity 74%；The SiO of the zeolite catalyst2With Al2O3Molar ratio is 27
When, the conversion ratio of the acrylic acid is 60%, acrylic acid selectivity 85%；The SiO of the zeolite catalyst2With Al2O3Rub
When your ratio is 48, the conversion ratio of the acrylic acid is 25%, acrylic acid selectivity 35%.Change in the zeolite catalyst
SiO2With Al2O3Molar ratio, the conversion ratio of lactate and the selectivity of acrylic acid in reaction result can change.
Such as 4 data of table it is found that SiO in the zeolite catalyst2/Al2O3Molar ratio significantly affects the ethyl lactate
Gas phase selectively dewatering reaction performance.
Embodiment 12
[catalyst preparation]
The concentration of KBr in embodiment 1 is changed to 0.01mol/L by 0.1mol/L, other preparation conditions and 1 phase of embodiment
Together, the catalyst being prepared is denoted as K0.54Na0.46ZSM-5_27。
[acrylic acid preparation]
Reaction condition is same as Example 3.Comparative example 3 and embodiment 12 are it is found that as K in catalyst zeolite+And Na+
Molar ratio when being reduced to 54/46 by 95/5, the selectivity of acrylic acid is 55%.
Embodiment 13
[catalyst preparation]
By SiO in embodiment 12/Al2O3Than being changed to SiO for 27 NaZSM-5 type zeolite2/Al2O3Than the Na β type boiling for 42
Stone, other preparation conditions are same as Example 1, and the catalyst being prepared is denoted as K0.95Na0.05β_42。
[acrylic acid preparation]
Reaction condition is same as Example 3, and gained reaction result is shown in Table 5.K0.95Na0.05Ethyl lactate on the catalyst of β _ 42
Conversion ratio be 50%, the selectivity of acrylic acid is 53%.
Embodiment 14
[catalyst preparation]
By SiO in embodiment 12/Al2O3Than being changed to SiO for 27 NaZSM-5 type zeolite2/Al2O3Than the NaMCM- for 26
22 type zeolites, other preparation conditions are same as Example 1, and the catalyst being prepared is denoted as K0.97Na0.03MCM-22_26。
[acrylic acid preparation]
Reaction condition is same as Example 3, and gained reaction result is shown in Table 5.K0.97Na0.03Lactic acid on MCM-22_26 catalyst
The conversion ratio of ethyl ester is 40%, and the selectivity of acrylic acid is 50%.
Embodiment 15
[catalyst preparation]
By SiO in embodiment 12/Al2O3Than being changed to SiO for 27 NaZSM-5 type zeolite2/Al2O3Than the NaMOR type for 20
Zeolite, other preparation conditions are same as Example 1, and the catalyst being prepared is denoted as K0.94Na0.06MOR_20。
[acrylic acid preparation]
Reaction condition is same as Example 3, and gained reaction result is shown in Table 5.K0.94Na0.06Lactic acid second on MOR_20 catalyst
The conversion ratio of ester is 10%, and the selectivity of acrylic acid is 30%.
Embodiment 16
[catalyst preparation]
By SiO in embodiment 12/Al2O3Than being changed to SiO for 27 NaZSM-5 type zeolite2/Al2O3Than the NaZSM- for 28
35 type zeolites, other preparation conditions are same as Example 1, and the catalyst being prepared is denoted as K0.90Na0.10ZSM-35_28。
[acrylic acid preparation]
Reaction condition is same as Example 3, and gained reaction result is shown in Table 5.K0.90Na0.10Lactic acid on ZSM-35_28 catalyst
The conversion ratio of ethyl ester is 30%, and the selectivity of acrylic acid is 10%.
Embodiment 17
[catalyst preparation]
By SiO in embodiment 12/Al2O3Than being changed to SiO for 27 NaZSM-5 type zeolite2/Al2O3Than the NaZSM- for 50
22 type zeolites, other preparation conditions are same as Example 1, and the catalyst being prepared is denoted as K0.96Na0.04ZSM-22_50。
[acrylic acid preparation]
Reaction condition is same as Example 3, and gained reaction result is shown in Table 5.K0.96Na0.04Lactic acid on ZSM-22_50 catalyst
The conversion ratio of ethyl ester is 20%, and the selectivity of acrylic acid is 30%.
Table 5, K+And Na+Exchange influence of the different zeolites catalyst to the dehydration of ethyl lactate
As shown in Table 5, the gas phase that the type of zeolite molecular sieve significantly affects the ethyl lactate on catalyst selectively takes off
The performance of water reaction, preferably comprises the zeolite of the ZSM-5 type skeleton.K+And Na+Ratio significantly affect the lactate
The selectivity of conversion ratio and acrylic acid, the preferably described K+And Na+Molar ratio be 50/50~100/0, with K+Ratio
It increases, the selectivity of acrylic acid improves.
Embodiment 18
[catalyst preparation]
It is 0.250molL by 150ml concentration in the case where 40 DEG C of water-baths and continuously stirring-1(NH4)2HPO4Aqueous solution is added drop-wise to
It is 0.251mol L equipped with 250ml concentration-1Ca (NO3)2·4H2In O aqueous solution, while the pH that concentrated ammonia liquor keeps solution is added dropwise
It is 10 ± 0.1；Continue to stir 1h after being added dropwise, gained precipitating suspension is placed in aging 12h in 40 DEG C of baking oven；Then it uses
Sand mold funnel filters to obtain white solid precipitated filter cakes, and filter cake is beaten with deionized water, stirring and washing, repeat this operation until
The conductivity of filtrate is less than 10 μ S cm-1Until；Last filter cake is dried overnight through 110 DEG C to be placed in tube furnace in moving air
(100ml min-1) in 360 DEG C of roasting 5h.The Ca/P ratio for the catalyst being prepared is 1.62, and maturing temperature is 360 DEG C and is denoted as
HAP1.62- 360 (calcium hydroxy phosphates).
[acrylic acid preparation]
Reaction condition is same as Example 3, and gained reaction result is shown in Table 6.HAP1.62- 360 (calcium hydroxy phosphate) catalyst
The conversion ratio of upper ethyl lactate is 65%, and the selectivity of acrylic acid is 52%.
Embodiment 19
[catalyst preparation]
By Ca (NO in embodiment 183)2·4H2The concentration of O aqueous solution is by 0.251mol L-1It is changed to 0.239mol L-1,
His preparation condition is identical as embodiment 18, and the catalyst Ca/P ratio being prepared is 1.60, and maturing temperature is 360 DEG C and is denoted as
HAP1.60- 360 (calcium hydroxy phosphates).
[acrylic acid preparation]
Reaction condition is same as Example 3, and gained reaction result is shown in Table 6.When the Ca/P ratio in calcium hydroxy phosphate is by 1.62
When dropping to 1.60, the selectivity of acrylic acid is 57%.
Embodiment 20
[catalyst preparation]
By Ca (NO in embodiment 183)2·4H2The concentration of O aqueous solution is by 0.251mol L-1It is changed to 0.263mol L-1,
His preparation condition is identical as embodiment 18, and the Ca/P ratio for the catalyst being prepared is 1.68, and maturing temperature is 360 DEG C and is prepared into
To catalyst be denoted as HAP1.68- 360 (calcium hydroxy phosphates).
[acrylic acid preparation]
Reaction condition is same as Example 3, and gained reaction result is shown in Table 6.When the Ca/P ratio in hydroxyapatite is by 1.62
When increasing to 1.68, the selectivity of acrylic acid is 42%.
Embodiment 21
[catalyst preparation]
The maturing temperature of sample in embodiment 18 is increased to 500 DEG C by 360 DEG C, other preparation conditions and 18 phase of embodiment
Together, the Ca/P ratio for the catalyst being prepared is 1.62, and maturing temperature is 500 DEG C and is denoted as HAP1.62- 500 (calcium hydroxy phosphates).
[acrylic acid preparation]
Reaction condition is same as Example 3, and gained reaction result is shown in Table 6.When the maturing temperature of hydroxyapatite is by 360 DEG C
When being increased to 500 DEG C, the selectivity of acrylic acid is 47%.
Embodiment 22
[catalyst preparation]
The maturing temperature of sample in embodiment 18 is increased to 700 DEG C by 360 DEG C, other preparation conditions and 18 phase of embodiment
Together, the Ca/P ratio for the catalyst being prepared is 1.62, and maturing temperature is that 700 DEG C of catalyst being prepared are denoted as HAP1.62-
700 (calcium hydroxy phosphates).
[acrylic acid preparation]
Reaction condition is same as Example 3, and gained reaction result is shown in Table 6.When the maturing temperature of calcium hydroxy phosphate is by 360 DEG C
When being increased to 700 DEG C, the selectivity of acrylic acid is 46%.
The dehydration performance of ethyl lactate on table 6, hydroxyapatite catalyst
No matter by table 6 it is found that the Ca/P or maturing temperature of the calcium hydroxy phosphate can significantly affect the lactic acid
The gas phase selectively dewatering reactivity worth of ethyl ester.When the ratio of the Ca/P of the calcium hydroxy phosphate is less than 1.68, with
The conversion ratio of the reduction of the ratio of Ca/P, the ethyl lactate gradually rises.
When the maturing temperature of the calcium hydroxy phosphate is less than 700 DEG C, the conversion ratio of the ethyl lactate is with calcination temperature
Decline, the conversion ratio of ethyl lactate gradually rise.Preferably, the lactate of the HAP1.60-360 (HAP is calcium hydroxy phosphate)
Conversion ratio reach 75%, the selectivity of acrylic acid reaches 57%.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
Limitations on the scope of the patent of the present invention therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention
Protect range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (13)
1. a kind of method for producing acrylic acid based on lactic acid aqueous solution of ester, which is characterized in that using lactic acid aqueous solution of ester as raw material,
Under the action of zeolite catalyst and/or hydroxyapatite catalyst, make the lactate that the reaction of gas phase selectively dewatering occur
Generate acrylic acid.
2. the method for producing acrylic acid according to claim 1 based on lactic acid aqueous solution of ester, which is characterized in that the cream
Acid esters aqueous solution is the mixing of methyl lactate aqueous solution, ethyl lactate aqueous solution or both.
3. the method for producing acrylic acid according to claim 1 based on lactic acid aqueous solution of ester, which is characterized in that the gas
The partial pressure of lactate described in phase selectivity dehydration is 10kPa hereinafter, the partial pressure of water is 10~50kPa.
4. the method for producing acrylic acid according to claim 1 based on lactic acid aqueous solution of ester, which is characterized in that the boiling
It include metal cation in stone catalyst, the metal cation includes alkali metal ion, alkaline-earth metal ions and rare earth metal
One or more of ion.
5. the method for producing acrylic acid according to claim 4 based on lactic acid aqueous solution of ester, which is characterized in that the alkali
Metal ion includes Li+、Na+、K+、Rb+、Cs+One of or it is a variety of, the alkaline-earth metal ions include Mg2+、Ca2+、Sr2+、
Ba2+One of or it is a variety of, the rare earth ion includes La3+、Ce4+One of or it is a variety of.
6. the method for producing acrylic acid according to claim 4 based on lactic acid aqueous solution of ester, which is characterized in that the boiling
The metal cation in stone catalyst is two kinds, and described two metal cations are Na+And K+、Na+And Rb+Or Na+And Cs+。
7. the method for producing acrylic acid according to claim 4 based on lactic acid aqueous solution of ester, which is characterized in that the boiling
The metal cation in stone catalyst is K+And Na+, the K+And Na+Molar ratio be 50/50~100/0.
8. the method for producing acrylic acid according to claim 1 based on lactic acid aqueous solution of ester, which is characterized in that the boiling
Stone catalyst includes one or more of ZSM-5, β, MCM-22, MOR, ZSM-22, ZSM-35 and X-type zeolite.
9. the method for producing acrylic acid according to claim 1 based on lactic acid aqueous solution of ester, which is characterized in that the boiling
Ratio >=0.8 of the total electrical charge number of metal cation and aluminium atom number in stone catalyst.
10. the method for producing acrylic acid according to claim 9 based on lactic acid aqueous solution of ester, which is characterized in that described
SiO in the zeolite skeleton of zeolite catalyst2/A12O3Molar ratio be 15~40.
11. the method for producing acrylic acid according to claim 1 based on lactic acid aqueous solution of ester, which is characterized in that described
Volume space velocity (GHSV) in the reaction of gas phase selectively dewatering is 1000h-1~9000h-1, reaction temperature is 300~400 DEG C.
12. the method for producing acrylic acid according to claim 1 based on lactic acid aqueous solution of ester, which is characterized in that described
Hydroxyapatite catalyst Formula is M10(XO4)6Y2, wherein M is bivalent cation Ca2+、Sr2+、Pb2+One of or it is a variety of；
XO4For PO4 3-、VO4 3-One of or it is a variety of；Y is OH-、F-In it is one or more.
13. the method for producing acrylic acid according to claim 1 based on lactic acid aqueous solution of ester, which is characterized in that described
Hydroxyapatite catalyst is calcium hydroxy phosphate, and the Ca/P molar ratio of the calcium hydroxy phosphate is≤1.67, the hydroxy-apatite
Maturing temperature≤700 DEG C in the preparation process of stone catalyst.
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| CN111715276A (en) * | 2020-06-24 | 2020-09-29 | 北方工业大学 | Preparation method of sponge copper-based composite catalytic material |
| CN116371461A (en) * | 2023-03-31 | 2023-07-04 | 北京化工大学 | Zeolite catalyst for preparing acrylic ester by catalyzing lactic acid ester dehydration and preparation method thereof |
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| CN116371461A (en) * | 2023-03-31 | 2023-07-04 | 北京化工大学 | Zeolite catalyst for preparing acrylic ester by catalyzing lactic acid ester dehydration and preparation method thereof |
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