CN114160116B - Zirconium catalyst based on steel slag, preparation method and application thereof in preparation of 1, 4-butanediol and co-production of methacrolein - Google Patents
Zirconium catalyst based on steel slag, preparation method and application thereof in preparation of 1, 4-butanediol and co-production of methacrolein Download PDFInfo
- Publication number
- CN114160116B CN114160116B CN202111313106.3A CN202111313106A CN114160116B CN 114160116 B CN114160116 B CN 114160116B CN 202111313106 A CN202111313106 A CN 202111313106A CN 114160116 B CN114160116 B CN 114160116B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- steel slag
- zirconium
- hydroxy
- methyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/65—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
- C07C45/66—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups by dehydration
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a zirconium catalyst based on steel slag, a preparation method and application thereof in preparing 1, 4-butanediol and co-producing methacrolein. The catalyst is rare earth element modified zirconium/steel slag solid superacid, contains zirconium element, rare earth element and steel slag, has the advantages of high specific surface area, high mechanical strength, low cost and the like, and can improve the catalytic reaction speed, the conversion rate of the reaction and the selectivity. The catalyst is used for the method for preparing 1, 4-butanediol and co-producing methacrolein by catalysis, improves the selective dehydration of 4-hydroxybutanal and 2-methyl-3-hydroxy-1-propanal, solves the problem that the byproduct 2-methyl-1, 3-propanediol is more in the existing 1, 4-butanediol preparation method, co-produces methacrolein, and improves the economy of the route for synthesizing 1, 4-butanediol by a propylene method.
Description
Technical Field
The invention relates to a zirconium catalyst based on steel slag, a preparation method and application thereof in preparing 1, 4-butanediol and co-producing methacrolein, belonging to the field of organic synthesis.
Background
1, 4-butanediol is an important basic organic chemical and fine chemical raw material, has wide application, and can be used as a raw material to derive various fine chemical products with high added value. For example, tetrahydrofuran (THF), gamma-butyrolactone (GBL), polybutylene terephthalate (PBT), polyurethane (PU) and the like can be produced, and in addition, 1, 4-butanediol itself can be used as a solvent, a raw material for paint and plasticizer, an intermediate for pharmaceutical production, a brightening agent in the plating industry and the like.
Thus, the 1, 4-butanediol is a chemical product with higher added value. In the existing industrial production, the propylene process route developed by Japanese colali company (GB 1493154A, US 4465873A) is mainly lyondel (CN 101084175B, WO2006068680A1, US2002111520A 1) and Taiwan Dalian chemical company (US 5426250A, TW 432037B) at present, and has the advantages of small investment, low energy consumption, flexible capacity adjustment and the like, but the propylene process is adopted to synthesize the 1, 4-butanediol, and the byproduct 2-methyl-1, 3-propanediol is generated, and the 2-methyl-1, 3-propanediol is used in a smaller amount than the 1, 4-butanediol, so that the demand is limited, and the propylene process route is greatly limited in scale due to the existence of the 2-methyl-1, 3-propanediol, so that the economy of the propylene process route is reduced.
Therefore, the existing propylene method for preparing the 1, 4-butanediol has the problems of large production amount of the byproduct 2-methyl-1, 3-propanediol and small market demand. Therefore, a preparation method of 1, 4-butanediol is needed to solve the problem of overlarge production of byproduct 2-methyl-1, 3-propanediol in the prior art.
Disclosure of Invention
Aiming at the problems in the prior art, one of the purposes of the invention is to provide a zirconium catalyst based on steel slag and a preparation method thereof, wherein the catalyst is a solid superacid, takes steel slag as a carrier, has the advantages of high specific surface area, high mechanical strength, low cost and the like, can promote the catalytic reaction speed, the conversion rate and the selectivity of the reaction, and is very suitable for the selective dehydration reaction of hydroxyaldehydes ketone, the dehydration product of which is conjugated unsaturated aldehyde ketone.
The invention also aims to provide a method for preparing 1, 4-butanediol co-production methacrolein by using the catalyst, which improves the selective dehydration of 4-hydroxybutanal and 2-methyl-3-hydroxy-1-propanal, solves the problem that the byproduct 2-methyl-1, 3-propanediol in the existing 1, 4-butanediol preparation method is more, and improves the economy of the route for synthesizing 1, 4-butanediol by using a propylene method.
To achieve the above object, the present invention provides the following solutions:
the invention provides a steel slag-based zirconium catalyst, which is rare earth element modified zirconium/steel slag solid superacid, and comprises 9-10% of zirconium element, 0.4-1% of rare earth element and 86-88% of steel slag by taking the total mass of the catalyst as 100%; preferably 9.17 to 9.22 percent of zirconium element, 0.461 to 0.917 percent of rare earth element and 86.68 to 87.09 percent of steel slag; the rest of the catalyst is oxygen element, and the zirconium element exists in the form of oxide.
Further, the steel slag-based zirconium catalyst disclosed by the invention comprises the following rare earth elements and zirconium elements in a mass ratio of 1:5 to 30, preferably 1:10 to 20.
Further, the zirconium-based catalyst based on steel slag has the acid strength range of preferably-11 < H o ＜-10。
Further, the steel slag-based zirconium catalyst of the present invention contains Bronsted acid (hereinafter referred to as B acid, which gives protons) and Lewis acid (hereinafter referred to as L acid, which accepts electrons) centers on the surface, and the acid amount ratio of B acid to L acid is preferably 8 < L/B < 10.
Further, the steel slag-based zirconium catalyst of the present invention, wherein the rare earth element is cerium (Ce) and/or lanthanum (La), preferably a mixture of cerium and lanthanum, more preferably cerium and lanthanum in a mass ratio of 1:0.5 to 1.5.
Further, the steel slag-based zirconium catalyst comprises, by mass, 100% of steel slag, 1-5% of iron element, 20-30% of calcium, 3-6% of magnesium, 9-11% of silicon, 3-4% of aluminum, 0.5-1% of manganese, 0.2-0.5% of phosphorus and 0.5-1% of titanium. Steel slag is a solid waste produced in steelmaking and mainly consists of calcium, iron, silicon, magnesium and a small amount of oxides of aluminum, manganese, phosphorus and the like. The main mineral phases are solid solution formed by oxides of tricalcium silicate, dicalcium silicate, calcium forsterite, calcium magnesium rosepside, calcium aluminoferrite, silicon, magnesium, iron, manganese and phosphorus, and also contain a small amount of free calcium oxide, metallic iron, fluorapatite and the like. In some areas, because the ore contains titanium and vanadium, the steel slag also contains a little of these components. The contents of various components in the steel slag are greatly different due to the steel-making furnace type, steel grade and different smelting stages of each furnace steel. In the invention, the catalytic effect of the invention can be realized only if the composition of the scrap steel slag meets the requirements.
Preferably, the steel slag particle size ranges from 1 to 5mm, more preferably D50 ranges from 2 to 4mm.
The invention also provides a preparation method of the steel slag-based zirconium catalyst, which comprises the following steps:
1) Dissolving soluble zirconium salt and soluble rare earth element salt in water, adding steel slag for soaking after the soluble zirconium salt and the soluble rare earth element salt are completely dissolved, then adjusting the pH value to 8-10 by ammonia water, separating precipitate, washing the precipitate with water until no chloride ions exist, and drying;
2) Soaking the precipitate in the step 1) by sulfuric acid solution, taking out, drying and roasting to obtain the steel slag-based zirconium catalyst.
In the process of the present invention, in step 1), the soluble zirconium salt is selected from zirconium oxychloride octahydrate (ZrOCl) 2 ·8H 2 O), anhydrous zirconium chloride (ZrCl) 4 ) Zirconium nitrate pentahydrate (Zr (NO) 3 ) 4 ·5H 2 O) any one or a combination of at least two, preferably zirconium oxychloride octahydrate;
the soluble salt of rare earth element is selected from one or a combination of at least two of hydrochloride and nitrate, preferably hydrochloride such as lanthanum chloride (LaCl) 3 ) Or alternativelyCerium chloride (CeCl) 3 )；
Preferably, the soluble zirconium salt is dissolved in water at a concentration of 0.001 to 0.2g/mL, preferably 0.01 to 0.1g/mL; the concentration of the soluble salt of the rare earth element dissolved in water is 0.0014-0.01 g/mL, preferably 0.0022-0.0070 g/mL.
In the method, in the step 1), the mass ratio of the soluble zirconium salt in the impregnating solution to the steel slag is 1:2.5 to 3, preferably 1:2.6 to 2.7;
Preferably, the impregnation time is from 0.5 to 5 hours, preferably from 1 to 2 hours.
In the method of the invention, in the step 1), the concentration of the ammonia water is 10 to 25 weight percent, preferably 15 to 20 weight percent;
the drying temperature is 100-120 ℃ and the drying time is 4-6 h.
In the method, in the step 2), when the sediment is immersed in the sulfuric acid solution, the mass ratio of the sediment to the sulfuric acid solution is 1:5-15, preferably 1:8-10;
preferably, the concentration of the sulfuric acid solution is 0.1-4 mol/L, preferably 1-2 mol/L, and the sulfuric acid solution is an aqueous solution of sulfuric acid;
preferably, the impregnation time is 1 to 3 hours.
In the method, in the step 2), the drying is carried out at the temperature of 100-120 ℃ for 4-6 hours; the roasting temperature is 500-700 ℃, preferably 575-625 ℃, and the time is 2-4 hours, preferably 2.5-3.5 hours.
The invention also provides application of the steel slag-based zirconium catalyst, which can be used for catalyzing dehydration reaction, esterification reaction, ether formation reaction and the like, and is particularly suitable for selective dehydration reaction, such as selective dehydration reaction for catalyzing 2-methyl-3-hydroxy-1-propanal.
Preferably, the invention provides a method for preparing 1, 4-butanediol and co-producing methacrolein, wherein the method adopts the steel slag-based zirconium catalyst, and comprises the following steps:
(1) The aqueous solution containing 4-hydroxy butyraldehyde and 2-methyl-3-hydroxy-1-propionaldehyde enters a reaction extraction tower filled with the steel slag-based zirconium catalyst, the 2-methyl-3-hydroxy-1-propionaldehyde is converted into isoolefine butyraldehyde through dehydration reaction, meanwhile, an organic extractant is added, the isoolefine butyraldehyde is obtained through extraction phase separation, and the aqueous solution containing 4-hydroxy butyraldehyde and unreacted 2-methyl-3-hydroxy-1-propionaldehyde is obtained from a raffinate phase;
(2) And (3) carrying out hydrogenation reaction on the raffinate phase obtained in the step (1) to convert 4-hydroxybutyraldehyde into 1, 4-butanediol.
In the step (1) of the invention, the aqueous solution containing 4-hydroxybutanal and 2-methyl-3-hydroxy-1-propanal is derived from an allyl alcohol hydroformylation process in the preparation of 1, 3-butanediol by a propylene method;
preferably, the aqueous solution containing 4-hydroxybutanal and 2-methyl-3-hydroxy-1-propanal comprises the following components: 10 to 20 weight percent of 4-hydroxy butyraldehyde, 1 to 2 weight percent of 2-methyl-3-hydroxy-1-propionaldehyde and 0.01 to 0.02 weight percent of propionaldehyde, and the balance being water.
In the step (1) of the present invention, the treatment amount of the steel slag-based zirconium catalyst is 1 to 10g of an aqueous solution containing 4-hydroxybutyraldehyde and 2-methyl-3-hydroxy-1-propanal/(g catalyst. H), preferably 2 to 5g of an aqueous solution containing 4-hydroxybutyraldehyde and 2-methyl-3-hydroxy-1-propanal/(g catalyst. H).
In the step (1) of the invention, the dehydration reaction is carried out at a reaction temperature of 70-150 ℃, preferably 100-120 ℃; the residence time is 0.01 to 0.5h, preferably 0.08 to 0.25h; the reaction pressure is normal pressure or slightly positive pressure, preferably 0 to 0.1MPaG. The reaction process needs to strictly control the temperature within the range of the invention, when the temperature is higher than 150 ℃, the dehydration reaction of 4-hydroxy butyraldehyde can be caused, the yield of 1, 4-butanediol is reduced, and when the temperature is lower than 70 ℃, the dehydration reaction of 2-methyl-3-hydroxy-1-propionaldehyde can be slowed down, so that the required aim of the invention is not achieved, and the proper reaction temperature needs to be controlled.
In the step (1), the conversion rate of the 2-methyl-3-hydroxy-1-propanal in the dehydration reaction is not less than 95%, and the selectivity is more than 99%; meanwhile, the conversion rate of the 4-hydroxy butyraldehyde is not higher than 1%.
In the step (1), the dehydration reaction is an equilibrium reaction, and the generated dehydration product methacrolein is easy to separate, so as to further accelerate the reaction rate, promote the reaction, reduce the separation cost, the dehydration reaction is carried out in a reaction extraction tower, so that the reaction and the separation steps are integrated, the product methacrolein can be continuously extracted and removed from the reaction system through an organic phase during production, the reaction is rapidly separated and promoted to right, and the theoretical plate number of the reaction extraction tower is 5-10.
In some embodiments of the invention, an aqueous solution containing 4-hydroxybutyraldehyde and 2-methyl-3-hydroxy-1-propanal is fed from above a catalyst layer in a reaction extraction tower with a catalyst in a certain mass ratio, an organic extractant is fed from below the catalyst layer in the reaction extraction tower, the catalyst catalyzes 2-methyl-3-hydroxy-1-propanal to carry out dehydration reaction to generate methacrolein, and the methacrolein generated by the reaction is extracted into the organic extractant while the dehydration reaction is carried out; an interface between the aqueous layer and the organic layer was formed at the bottom of the column, and an aqueous solution (raffinate phase) containing 4-hydroxybutyraldehyde and unreacted 2-methyl-3-hydroxy-1-propanal was continuously withdrawn from the bottom of the column, while an organic phase (extract phase) containing methacrolein was continuously withdrawn, so that the interface position was kept unchanged. In some embodiments of the invention, the extraction section of the reactive extraction column is heated to effect reactive extraction. In some preferred embodiments, the outer periphery of the reactive extraction column is jacketed for heating or maintaining the reactive extraction column by heating the jacket of the outer periphery of the reactive extraction column, more preferably the outer periphery of the column packed with catalyst.
In the step (1) of the present invention, the organic extractant is a water-insoluble organic substance selected from one or more of aromatic hydrocarbon compounds such as toluene and xylene, aliphatic hydrocarbon compounds such as cyclohexane and heptane, ether compounds such as diethyl ether and butyl ether, preferably aromatic hydrocarbon compounds such as toluene and xylene, more preferably toluene;
preferably, the mass ratio of the organic extractant to the aqueous solution containing 4-hydroxybutyraldehyde and 2-methyl-3-hydroxy-1-propanal is 1:1-10, preferably 1:4-6.
In the step (2), the aqueous solution containing 4-hydroxybutanal and unreacted 2-methyl-3-hydroxy-1-propanal continuously extracted from the bottom of the extraction tower is further subjected to hydrogenation reaction to obtain a reaction product 1, 4-butanediol, wherein the hydrogenation reaction is carried out at the temperature of 125-135 ℃ under the pressure of 3-8 MPa for 0.5-2 hours, and a crude hydrogenation reaction solution is obtained after the reaction is finished.
Preferably, the hydrogenation reaction is carried out under the condition of a catalyst, and the catalyst can be any hydrogenation catalyst disclosed in the prior art, preferably a Raney nickel catalyst (such as Raney 6800) and the like, more preferably, the catalyst is used in an amount of 1-5%, preferably 2-3% by mass of an aqueous solution containing 4-hydroxybutyraldehyde and unreacted 2-methyl-3-hydroxy-1-propanal.
According to the method, after the reaction is completed, the steps (1) and (2) further comprise separation operation, so that high-purity methacrolein and 1, 4-butanediol products are obtained.
Preferably, the extract phase in the step (1) is separated by normal pressure rectification to obtain methacrolein, in the normal pressure rectification process, the number of tower plates of a rectifying tower is 8-10, the methacrolein product is obtained by collecting fractions at 68.5-69.5 ℃, the organic extractant is obtained by collecting fractions at 110-111 ℃, and the separated organic extractant can be returned to the reaction extraction tower in the step (1) for recycling.
The final yield of the separated methacrolein product is more than 90 percent based on 2-methyl-3-hydroxy-1-propanal, and the purity of the methacrolein product is more than or equal to 99.00 percent.
Preferably, in the step (2), crude hydrogenation reaction liquid obtained by hydrogenation reaction is separated by vacuum rectification to obtain 1, 4-butanediol, in the vacuum rectification process, the tower plate number of a rectifying tower is 20-25, firstly, low boiling point compounds such as water, isobutanol and butanol are separated by collecting fractions with the pressure of 5-20 Kpa and the temperature of 30-80 ℃, and then, the 1, 4-butanediol product is obtained by collecting fractions with the pressure of 1.9-2.1 Kpa and the temperature of 124-126 ℃.
The final yield of the 1, 4-butanediol product obtained by separation is more than 95%, and the purity of the 1, 4-butanediol product is more than or equal to 99.95%.
The dehydration reaction of 4-hydroxybutanal and 2-methyl-3-hydroxy-1-propanal is simultaneously involved in the step (1) of the invention, and the dehydration reaction is shown in the following formula:
the dehydration reaction product of 2-methyl-3-hydroxy-1-propanal is a conjugated structure, which is more likely to occur, than that of 4-hydroxybutyraldehyde, and the inventors found that 2-methyl-3-hydroxy-1-propanal can be dehydrated as much as possible without or with little reaction of 4-hydroxybutyraldehyde by appropriate reaction conditions. The method can obviously reduce the production of the byproduct 2-methyl-1, 3-propanediol, wherein the conversion rate of the 2-methyl-3-hydroxy-1-propanal to the methacrolein is not lower than 95 percent, and the conversion rate of the 4-hydroxy butanal to the methacrolein is not higher than 1 percent. The yield of 2-methyl-1, 3-propanediol is reduced from 10-15 ten thousand tons per year to 0.5-1 ten thousand tons per year calculated by using 100 ten thousand tons per year of 1, 4-butanediol, the economical efficiency of the route is greatly improved, the byproduct methacrolein is an important chemical raw material, can be used as a production raw material of methacrylic acid and a thermoplastic monomer raw material, and can be used as a raw material for producing isoprene glycol through selective hydrogenation.
In order to achieve the aim, the invention develops a solid super acidic catalyst, which adopts steel slag as a carrier, has the advantages of large specific surface area, high hardness, strong stability and the like, can improve the content of active centers of the catalyst, improve the catalytic efficiency of the catalyst and prolong the service life of the catalyst; in addition, the steel slag contains alkaline metal elements such as calcium, magnesium, manganese and the like, so that the effect of proper acid strength adjustment can be achieved in the process of preparing the super acid, the dehydration reaction of the 2-methyl-3-hydroxy-1-propanal is ensured to be catalyzed, the dehydration reaction of the 4-hydroxy butanal can be effectively inhibited, and the reaction selectivity is improved. The solid super acid of the invention can reduce the acid strength after being further modified by rare earth elements, and the special electronic action of the rare earth elements is applied to SO 4 2- The non-bridging oxygen in the catalyst has an accumulation effect and can stabilize SO on the surface of the catalyst 4 2- Increase the number of acid site centers of the catalyst and promote catalysisThe catalyst has the advantages that the stability of the catalyst is improved, compared with a catalyst without rare earth modification under the same condition, the adsorption capacity of solid acid to structural water is improved by introducing rare earth elements, the existence of structural water is favorable for converting an L acid center into a B acid center, and for the solid acid catalyst, the acidity of the B acid center is weaker than that of the L acid, but the B acid center has better deactivation resistance, so that the solid superacid modified by the rare earth elements has moderate acidity and increased active center, and the dehydration reaction of 4-hydroxy butyraldehyde is effectively controlled while the dehydration reaction of 2-methyl-3-hydroxy-1-propionaldehyde is catalyzed, so that the expected effect is achieved. Meanwhile, the dosage of rare earth elements needs to be strictly controlled, the dosage of rare earth elements is too low, the modification meaning of super acid is not great, the dosage of rare earth elements is too great, the activity of the catalyst is reduced, the main reason is that the catalyst is added with a proper amount of rare earth, which is equivalent to placing an electron source near the catalyst, so that Zr is generated 2+ The positive charge of the ion increases, changing the chemical state of the atoms on the catalyst surface, and the Lewis acid center density on the catalyst surface increases. When the rare earth is excessively used, the ZrO in the crystal lattice is reduced 2 The content of the modified organic compound covers part of L acid position and causes the modification of the electronic shift condition of S=O bond, SO that SO on unit surface is reduced 4 2- The number of acid centers is reduced, resulting in a decrease in activity.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
1) The invention creatively adopts a reactive extraction system, utilizes the difference of dehydration activities of 4-hydroxy butyraldehyde and 2-methyl-3-hydroxy-1-propionaldehyde in raw materials, adopts a steel slag-based zirconium catalyst to selectively dehydrate 2-methyl-3-hydroxy-1-propionaldehyde to generate methacrolein, solves the problem of more byproduct 2-methyl-1, 3-propanediol in the existing preparation method, and coproduces methacrolein, thereby improving the economy of the route for synthesizing 1, 4-butanediol by a propylene method.
2) The steel slag is used as a catalyst carrier, so that waste is changed into valuable, and the resource utilization rate is improved.
3) The 1, 4-butanediol prepared by the method has simple operation and small investment, and is suitable for industrial production.
Detailed Description
The invention will now be further illustrated by means of specific examples which are given solely by way of illustration of the invention and do not limit the scope thereof.
The main raw material source information adopted in the examples:
steel slag: the composition of the alloy steel group comprises 3 weight percent of iron element, 26.5 weight percent of calcium, 5.7 weight percent of magnesium, 10.8 weight percent of silicon, 3.9 weight percent of aluminum, 0.78 weight percent of manganese, 0.3 weight percent of phosphorus and 0.77 weight percent of titanium, the grain size is 1-5 mm, and the D50 is 2-4 mm.
An aqueous solution containing 4-hydroxybutyraldehyde, 2-methyl-3-hydroxy-1-propanal: prepared as described in example 1 of chinese patent (CN 103657727 a), the resulting reaction mixture was extracted with water at a mass ratio of 1:1 to give a composition comprising 18wt% 4-hydroxybutyraldehyde, 1.8wt% 2-methyl-3-hydroxy-1-propanal, and 0.015wt% propanal with the remainder being water.
Unless otherwise specified, other materials according to the present invention are commercially available.
The gas chromatographic analysis used in the examples of the present invention was performed according to the following method: 30m DB-WAX, ID: 0.32mm, FD: 0.25 μm;80-230 ℃,3 ℃/min, nitrogen flow rate: 30mL/min, hydrogen flow rate: 40mL/min, air flow rate: 400mL/min; sample injection amount: 0.2. Mu.L. GC was tested using Agilent7820 and samples were diluted 3-fold with chromatographic methanol.
Infrared was tested using Nicolet Nexus 470.
Determination method of acid amount ratio of B acid to L acid (L/B) in carrier: removing adsorbed water from the carrier to be tested, performing sufficient physical and chemical adsorption with pyridine, desorbing physically adsorbed pyridine at 300deg.C under vacuum, and measuring infrared spectrum of the carrier, and measuring L acid center (1446.2 cm) -1 ) Acid center B (1546.2 cm) -1 ) L/B is the ratio of the peak areas of the infrared spectrogram.
Acid strength H o Is determined by the following steps: adding a small amount of an indicator B (m-nitrotoluene, an extremely weak base) into the measured sample, wherein the B is conjugated with protons to form a conjugated acid BH + Having different colours, according to[ B ] when the acid-base reaction reaches equilibrium]/[BH + ]The value can be obtained to obtain H 0 ：H 0 ＝P K BH+ -lg([BH + ]/[B])
P K BH+ ＝-lg(K BH+ )
Wherein K is BH+ Is a chemical reaction BH + →B+H + Is a constant of equilibrium of (a).
Example 1
The preparation method of the steel slag-based zirconium catalyst comprises the following steps:
1) 161g ZrOCl 2 ·8H 2 O、5.373gCeCl 3 And 2.683g LaCl 3 Dissolving in 1000g of water, adding 430g of steel slag after the dissolution is completed, and soaking for 1h; then ammonia water with the mass fraction of 20wt% is added dropwise under stirring to adjust the pH to about 9. The precipitate was filtered off with suction and washed with a large amount of distilled water until free of chloride ions, and dried at 110℃for 5h.
2) Immersing 430g of dried precipitate solid into 3920g of sulfuric acid aqueous solution with the concentration of 2mol/L for 2 hours, drying at 110 ℃ for 5 hours, and roasting at 600 ℃ for 3 hours to obtain the rare earth element modified steel slag-based zirconium catalyst.
Determining the composition of the catalyst and the acid quantity ratio L/B of the B acid to the L acid, and determining the acid strength H of different carriers by adopting an indicator method o The results are shown in Table 1.
Example 2
The preparation method of the steel slag-based zirconium catalyst comprises the following steps:
1) 193.2g ZrOCl 2 ·8H 2 O、3.204gCeCl 3 And 3.222g LaCl 3 Dissolving in 1320g of water, adding 516g of steel slag after the dissolution is completed, and soaking for 1.5h; then ammonia water with the mass fraction of 20wt% is added dropwise under stirring to adjust the pH to 8. The precipitate was filtered off with suction and washed with a large amount of distilled water until free of chloride ions, and dried at 100℃for 6 hours.
2) And immersing 516g of dried precipitate solid into 4410g of sulfuric acid aqueous solution with the concentration of 1.5mol/L for 2h, drying at 120 ℃ for 4h, and roasting at 575 ℃ for 4h to obtain the rare earth element modified steel slag-based zirconium catalyst.
The catalyst was tested in the same manner as in example 1, and the results are shown in Table 1.
Example 3
The preparation method of the steel slag-based zirconium catalyst comprises the following steps:
1) 209.3g ZrOCl were added 2 ·8H 2 O、2.085gCeCl 3 、3.136g LaCl 3 Dissolving in 1560g of water, adding 559g of steel slag after the dissolution is completed, and soaking for 2 hours; then ammonia water with the mass fraction of 20wt% is added dropwise under stirring to adjust the pH to 10. The precipitate was filtered off with suction and washed with a large amount of distilled water until free of chloride ions, and dried at 120℃for 4h.
2) Taking 559g of dried precipitate solid, immersing the precipitate solid into 4900g of 1mol/L sulfuric acid aqueous solution for 3h, drying the precipitate solid at 100 ℃ for 6h, and roasting the precipitate solid at 625 ℃ for 2h to obtain the rare earth element modified steel slag-based zirconium catalyst.
The catalyst was tested in the same manner as in example 1, and the results are shown in Table 1.
Example 4
The preparation method of the steel slag-based zirconium catalyst comprises the following steps:
1) 185.15g ZrOCl were added 2 ·8H 2 O、5.534gCeCl 3 、3.703g LaCl 3 Dissolving in 1495g of water, adding 494.5g of steel slag after the dissolution is completed, and soaking for 1h; then ammonia water with the mass fraction of 20wt% is added dropwise under stirring to adjust the pH to 9. The precipitate was filtered off with suction and washed with a large amount of distilled water until free of chloride ions, and dried at 110℃for 5h.
2) And immersing 494g of dried precipitate solid into 4900g of 1mol/L sulfuric acid aqueous solution for 1h, drying at 120 ℃ for 4h, and roasting at 600 ℃ for 3h to obtain the rare earth element modified steel slag-based zirconium catalyst.
The catalyst was tested in the same manner as in example 1, and the results are shown in Table 1.
Example 5
The preparation method of the steel slag-based zirconium catalyst comprises the following steps:
1) 161g ZrOCl 2 ·8H 2 O、5.370g LaCl 3 Dissolving in 1400g of waterAdding 430g of steel slag after complete dissolution, and soaking for 1.5 hours; then ammonia water with the mass fraction of 20wt% is added dropwise under stirring to adjust the pH to 10. The precipitate was filtered off with suction and washed with a large amount of distilled water until free of chloride ions, and dried at 100℃for 6 hours.
2) Immersing 430g of dried precipitate solid into 3920g of sulfuric acid aqueous solution with the concentration of 2mol/L for 2 hours, drying at 110 ℃ for 5 hours, and roasting at 600 ℃ for 3 hours to obtain the rare earth element modified steel slag-based zirconium catalyst.
The catalyst was tested in the same manner as in example 1, and the results are shown in Table 1.
Example 6
The preparation method of the steel slag-based zirconium catalyst comprises the following steps:
1) 161g ZrOCl 2 ·8H 2 O、4.010g CeCl 3 Dissolving in 1400g of water, adding 430g of steel slag after the steel slag is completely dissolved, and soaking for 2h; then ammonia water with the mass fraction of 20wt% is added dropwise under stirring to adjust the pH to 9. The precipitate was filtered off with suction and washed with a large amount of distilled water until free of chloride ions, and dried at 110℃for 5h.
2) Immersing 430g of dried precipitate solid into 4410g of sulfuric acid aqueous solution with the concentration of 1.5mol/L for 2h, drying at 120 ℃ for 4h, and roasting at 600 ℃ for 3h to obtain the rare earth element modified steel slag-based zirconium catalyst.
The catalyst was tested in the same manner as in example 1, and the results are shown in Table 1.
Comparative example 1
With reference to example 1, the only difference is that no rare earth element (i.e., no CeCl) is added during the preparation process 3 And LaCl 3 ) The zirconium-based catalyst was obtained.
The catalyst was tested in the same manner as in example 1, and the results are shown in Table 1.
Comparative example 2
The preparation method of the steel slag-based zirconium catalyst comprises the following steps:
1) 161g ZrOCl 2 ·8H 2 O、80.480g LaCl 3 Dissolving in 1000g of water, adding 430g of steel slag after the dissolution is completed, and soaking for 1h; then in the stirring bar Dropwise adding ammonia water with mass fraction of 20wt% under the piece to adjust the pH to about 8. The precipitate was filtered off with suction and washed with a large amount of distilled water until free of chloride ions, and dried at 110℃for 5h.
2) And immersing 490g of dried precipitate solid into 3920g of sulfuric acid aqueous solution with the concentration of 2mol/L for 2 hours, drying at 110 ℃ for 5 hours, and roasting at 600 ℃ for 3 hours to obtain the rare earth element modified steel slag-based zirconium catalyst.
The catalyst was tested in the same manner as in example 1, and the results are shown in Table 1.
Comparative example 3
With reference to example 1, the zirconium-based catalyst was prepared only by replacing the carrier steel slag with an MCM-41 type molecular sieve of equal mass.
The catalyst was tested in the same manner as in example 1, and the results are shown in Table 1.
Comparative example 4
With reference to example 1, the zirconium-based catalyst was prepared only by replacing the carrier steel slag with activated alumina pellets of equal mass.
The catalyst was tested in the same manner as in example 1, and the results are shown in Table 1.
Comparative example 5
With reference to example 1, a zirconium-based catalyst was prepared by replacing the carrier steel slag with an equal mass of iron ore.
The catalyst was tested in the same manner as in example 1, and the results are shown in Table 1.
Comparative example 6
With reference to example 1, the zirconium-based catalyst was prepared by replacing the carrier steel slag with diatomaceous earth of equal mass.
The catalyst was tested in the same manner as in example 1, and the results are shown in Table 1.
Table 1 examples 1-6 catalyst composition
Example 7
The method for preparing 1, 4-butanediol and co-producing methacrolein comprises the following steps:
(1) The extraction column was packed with 400g of the catalyst prepared in the previous example 1, the inner diameter of the extraction column was 25mm and the length was 1000mm; the temperature of the jacket of the extraction column was kept at 100 ℃, the extraction column was first filled with water, then an aqueous solution containing 4-hydroxybutyraldehyde and 2-methyl-3-hydroxy-1-propanal was continuously fed from the column top at a feed rate of 800g/h (liquid space velocity whsv=2.0 g/gcat/h), toluene was continuously fed from the column bottom at a feed rate of 200g/h (mass ratio to the aqueous solution containing 4-hydroxybutyraldehyde and 2-methyl-3-hydroxy-1-propanal was 1:4), and an interface between the aqueous layer and the organic layer was made in the vicinity of the column bottom so that the interface position was not changed, and an aqueous solution (raffinate phase) containing 4-hydroxybutyraldehyde and unreacted 2-methyl-3-hydroxy-1-propanal was continuously withdrawn from the column top. During operation, the temperature in the column was controlled to 100 ℃ by adjusting the external jacket temperature. Sampling GC analysis is carried out during feeding, the reaction reaches equilibrium after 10 hours, the conversion rate of 2-methyl-3-hydroxy-1-propanal to methacrolein is calculated to be 96.19%, the selectivity is 99.08%, and the conversion rate of 4-hydroxybutanal to methacrolein is calculated to be 0.845%.
Separating the extraction phase by normal pressure rectification, collecting the fraction at 68.5-69.5 ℃ by 8 column plates of a rectifying tower to obtain an methacrolein product, collecting the fraction at 110-111 ℃ to obtain an organic extractant, and returning the separated organic extractant to the reaction extraction tower in the step (1) for recycling. The final yield of the separated methacrolein product was 93.4% and the purity of the methacrolein product was 99.02% based on 2-methyl-3-hydroxy-1-propanal.
(2) To 400g of an aqueous phase (raffinate phase) of an aqueous solution containing 4-hydroxybutyraldehyde and unreacted 2-methyl-3-hydroxy-1-propanal, 10g of Raney nickel catalyst (Raney 6800) was added, and the mixture was placed in a reaction vessel, and subjected to hydrogenation under a pressure of 5MPa at a temperature of 130℃for 1.5 hours to obtain a crude hydrogenation reaction solution.
Separating the crude hydrogenation reaction liquid by vacuum rectification, wherein the number of tower plates of a rectifying tower is 20, firstly, separating water, isobutanol, butanol and other low boiling point compounds by collecting fractions with the pressure of 5-20 Kpa and the temperature of 30-80 ℃, and then, obtaining a 1, 4-butanediol product by collecting fractions with the pressure of 1.9-2.1 Kpa and the temperature of 124-126 ℃. The final yield of the separated 1, 4-butanediol product is 95.2%, and the purity of the 1, 4-butanediol product is 99.951%.
Example 8
The procedure of example 7 was followed, except that the following differences:
The catalyst prepared in example 7 in example 1 was replaced with the catalyst prepared in example 2, the temperature in the column was controlled to 110℃and the mass ratio of toluene to the aqueous solution containing 4-hydroxybutyraldehyde and 2-methyl-3-hydroxy-1-propanal was 1:6, with the space velocity WHSV=3.0 g/gcat/h of the aqueous solution containing 4-hydroxybutyraldehyde and 2-methyl-3-hydroxy-1-propanal. Sampling and GC analysis is carried out during feeding, the reaction reaches equilibrium after 8 hours, the conversion rate of 2-methyl-3-hydroxy-1-propanal to methacrolein is calculated to be 96.37 percent, the selectivity is 99.06 percent, and the conversion rate of 4-hydroxybutanal to methacrolein is calculated to be 0.907 percent; the final yield of the methacrolein product is 92.6%, the purity of the methacrolein product is 99.12%, the final yield of the 1, 4-butanediol product is 95.8%, and the purity of the 1, 4-butanediol product is 99.953%.
Example 9
The procedure of example 7 was followed, except that the following differences:
the catalyst prepared in example 7 in example 1 was replaced with the catalyst prepared in example 3, the temperature in the column was controlled to 120℃and the mass ratio of toluene to the aqueous solution containing 4-hydroxybutyraldehyde and 2-methyl-3-hydroxy-1-propanal was 1:5, with the space velocity WHSV=4.0 g/gcat/h of the aqueous solution containing 4-hydroxybutyraldehyde and 2-methyl-3-hydroxy-1-propanal. Sampling and GC analysis is carried out during feeding, the reaction reaches equilibrium after 5 hours, the conversion rate of 2-methyl-3-hydroxy-1-propanal to methacrolein is calculated to be 96.29 percent, the selectivity is 99.12 percent, and the conversion rate of 4-hydroxybutanal to methacrolein is calculated to be 0.878 percent; the final yield of the methacrolein product is 94.2%, the purity of the methacrolein product is 99.02%, the final yield of the 1, 4-butanediol product is 96.2%, and the purity of the 1, 4-butanediol product is 99.950%.
Example 10
The procedure of example 7 was followed, except that the following differences:
the catalyst 1 prepared in example 7 was replaced with the catalyst prepared in example 4, the temperature in the column was controlled to 100℃and the mass ratio of toluene to the aqueous solution containing 4-hydroxybutyraldehyde and 2-methyl-3-hydroxy-1-propanal was 1:5, with the space velocity WHSV=3.0 g/gcat/h of the aqueous solution containing 4-hydroxybutyraldehyde and 2-methyl-3-hydroxy-1-propanal. Sampling and GC analysis is carried out during feeding, the reaction reaches equilibrium after 7 hours, the conversion rate of 2-methyl-3-hydroxy-1-propanal to methacrolein is calculated to be 95.85 percent, the selectivity is 99.17 percent, and the conversion rate of 4-hydroxybutanal to methacrolein is calculated to be 0.764 percent; the final yield of the methacrolein product is 92.1%, the purity of the methacrolein product is 99.32%, the final yield of the 1, 4-butanediol product is 95.4%, and the purity of the 1, 4-butanediol product is 99.957%.
Example 11
The procedure of example 7 was followed, except that the following differences:
the catalyst 1 prepared in example 7 was replaced with the catalyst prepared in example 5, the temperature in the column was controlled to 110℃and the mass ratio of toluene to the aqueous solution containing 4-hydroxybutyraldehyde and 2-methyl-3-hydroxy-1-propanal was 1:4, with the space velocity WHSV=4.0 g/gcat/h of the aqueous solution containing 4-hydroxybutyraldehyde and 2-methyl-3-hydroxy-1-propanal. Sampling GC analysis during feeding, and after 9 hours, the reaction reaches equilibrium, the conversion rate of 2-methyl-3-hydroxy-1-propanal to methacrolein is 92.41 percent, the selectivity is 99.39 percent, and the conversion rate of 4-hydroxybutanal to methacrolein is 0.901 percent. The final yield of the methacrolein product is 82.7%, the purity of the methacrolein product is 99.37%, the final yield of the 1, 4-butanediol product is 96.1%, and the purity of the 1, 4-butanediol product is 99.961%.
Example 12
The procedure of example 7 was followed, except that the following differences:
the catalyst 1 prepared in example 7 was replaced with the catalyst prepared in example 6, the temperature in the column was controlled to 120℃and the mass ratio of toluene to the aqueous solution containing 4-hydroxybutyraldehyde and 2-methyl-3-hydroxy-1-propanal was 1:6, with the space velocity WHSV=5.0 g/gcat/h of the aqueous solution containing 4-hydroxybutyraldehyde and 2-methyl-3-hydroxy-1-propanal. Sampling GC analysis during feeding, after 5 hours, the reaction reaches equilibrium, the conversion rate of 2-methyl-3-hydroxy-1-propanal to methacrolein is calculated to be 85.43%, the selectivity is 99.34%, the conversion rate of 4-hydroxybutanal to methacrolein is calculated to be 0.921%, the final yield of methacrolein product is 79.8%, the purity of methacrolein product is 99.09%, the final yield of 1, 4-butanediol product is 96.4%, and the purity of 1, 4-butanediol product is 99.957%.
Comparative example 7
The procedure of example 7 was followed, except that the following differences:
the catalyst prepared from example 1 in example 7 was replaced with the catalyst prepared from comparative example 1. After 9h the reaction reaches equilibrium, and the conversion of 2-methyl-3-hydroxy-1-propanal to methacrolein is 97.97% and the conversion of 4-hydroxybutyraldehyde to crotonaldehyde is 34.921%. The final yield of the methacrolein product is 90.30%, the purity of the methacrolein product is 97.09%, the final yield of the 1, 4-butanediol product is 51.56%, and the purity of the 1, 4-butanediol product is 99.967%.
Comparative example 8
The procedure of example 7 was followed, except that the following differences:
the catalyst 1 prepared from example 1 in example 7 was replaced with the catalyst prepared in comparative example 2 described previously. After 9 hours, the reaction reaches equilibrium, the conversion rate of 2-methyl-3-hydroxy-1-propanal to methacrolein is calculated to be 32.17%, and the conversion rate of 4-hydroxybutyraldehyde to methacrolein is calculated to be 0.427%. The final yield of the methacrolein product is 21.45%, the purity of the methacrolein product is 99.19%, the final yield of the 1, 4-butanediol product is 93.24%, and the purity of the 1, 4-butanediol product is 99.947%.
Comparative example 9
The procedure of example 7 was followed, except that the following differences:
using the catalyst 1 prepared in example 1 in example 7, the reaction extraction system was replaced with a tubular reactor, an aqueous solution containing 4-hydroxybutyraldehyde and 2-methyl-3-hydroxy-1-propanal was fed at 800g/h (liquid space velocity WHSV=2.0 g/gcat/h), and after 9 hours the reaction was equilibrated, the conversion rate of 2-methyl-3-hydroxy-1-propanal to methacrolein was calculated to be 27.33%, and the conversion rate of 4-hydroxybutyraldehyde to methacrolein was calculated to be 0.427%. The final yield of the methacrolein product is 18.86%, the purity of the methacrolein product is 99.01%, the final yield of the 1, 4-butanediol product is 95.68%, and the purity of the 1, 4-butanediol product is 99.932%.
Comparative example 10
The procedure of example 7 was followed, except that the following differences:
the catalyst 1 prepared from example 1 in example 7 was replaced with the catalyst prepared in the preparation comparative example 3 described previously. After 9 hours, the reaction reaches equilibrium, the conversion rate of the 2-methyl-3-hydroxy-1-propanal to methacrolein is calculated to be 99.04%, and the conversion rate of the 4-hydroxybutyraldehyde to methacrolein is calculated to be 57.32%. The final yield of the methacrolein product is 91.30%, the purity of the methacrolein product is 96.08%, the final yield of the 1, 4-butanediol product is 39.89%, and the purity of the 1, 4-butanediol product is 99.969%.
Comparative example 11
The procedure of example 7 was followed, except that the following differences:
the catalyst 1 prepared from example 1 in example 7 was replaced with the catalyst prepared in the preparation comparative example 4 described previously. After 7 hours, the reaction reaches equilibrium, the conversion rate of the 2-methyl-3-hydroxy-1-propanal to methacrolein is 99.20% and the conversion rate of the 4-hydroxybutyraldehyde to methacrolein is 47.97%. The final yield of the methacrolein product is 91.36%, the purity of the methacrolein product is 96.89%, the final yield of the 1, 4-butanediol product is 43.14%, and the purity of the 1, 4-butanediol product is 99.964%.
Comparative example 12
The procedure of example 7 was followed, except that the following differences:
The catalyst 1 prepared from example 1 in example 7 was replaced with the catalyst prepared in the preparation comparative example 5 described previously. After 9 hours, the reaction reaches equilibrium, the conversion rate of the 2-methyl-3-hydroxy-1-propanal to methacrolein is 99.20% and the conversion rate of the 4-hydroxybutyraldehyde to methacrolein is 57.67%. The final yield of the methacrolein product is 92.37%, the purity of the methacrolein product is 96.45%, the final yield of the 1, 4-butanediol product is 33.14%, and the purity of the 1, 4-butanediol product is 99.967%.
Comparative example 13
The procedure of example 7 was followed, except that the following differences:
the catalyst 1 prepared from example 1 in example 7 was replaced with the catalyst prepared in the preparation comparative example 6 described previously. After 10 hours, the reaction reaches equilibrium, the conversion rate of the 2-methyl-3-hydroxy-1-propanal to methacrolein is 99.20% and the conversion rate of the 4-hydroxybutyraldehyde to methacrolein is 37.97%. The final yield of the methacrolein product was 92.34%, the purity of the methacrolein product was 97.09%, the final yield of the 1, 4-butanediol product was 53.98%, and the purity of the 1, 4-butanediol product was 99.967%.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and additions may be made to those skilled in the art without departing from the method of the present invention, which modifications and additions are also to be considered as within the scope of the present invention.
Claims (37)
1. A steel slag-based zirconium catalyst is characterized in that the catalyst is a rare earth element modified zirconium steel slag solid superacid, and the surface of the catalyst contains SO 4 2- The catalyst comprises 9-10% of zirconium element, 0.4-1% of rare earth element and 86-88% of steel slag by taking the total mass of the catalyst as 100%.
2. The catalyst according to claim 1, wherein the catalyst composition comprises 9.17-9.22% of zirconium element, 0.461-0.917% of rare earth element and 86.68-87.09% of steel slag.
3. The catalyst according to claim 1, wherein the mass ratio of the rare earth element to the zirconium element is 1:5 to 30.
4. A catalyst according to claim 3, wherein the mass ratio of rare earth element to zirconium element is 1:10 to 20.
5. The catalyst according to claim 1, wherein the steel slag-based zirconium-based catalyst has an acid strength of-11 < H o ＜-10。
6. The catalyst according to claim 1, wherein the slag-based zirconium-based catalyst contains an acid amount ratio of bronsted acid to lewis acid of 8 < L/B < 10.
7. The catalyst according to claim 1, characterized in that the rare earth element is cerium and/or lanthanum.
8. The catalyst of claim 7 wherein the rare earth element is a mixture of cerium and lanthanum.
9. The catalyst according to claim 8, wherein the rare earth elements are cerium and lanthanum in a mass ratio of 1:0.5 to 1.5.
10. The catalyst according to claim 1, wherein the steel slag comprises, based on 100% by mass, 1 to 5% by weight of iron element, 20 to 30% by weight of calcium, 3 to 6% by weight of magnesium, 9 to 11% by weight of silicon, 3 to 4% by weight of aluminum, 0.5 to 1% by weight of manganese, 0.2 to 0.5% by weight of phosphorus, and 0.5 to 1% by weight of titanium.
11. The catalyst of claim 1, wherein the steel slag has a particle size in the range of 1 to 5mm.
12. The catalyst of claim 11, wherein the steel slag particle size D50 is 2-4 mm.
13. A method for preparing the steel slag-based zirconium catalyst according to any one of claims 1 to 12, comprising the steps of:
1) Dissolving soluble zirconium salt and soluble rare earth element salt in water, adding steel slag for soaking after the soluble zirconium salt and the soluble rare earth element salt are completely dissolved, then adjusting the pH value to 8-10 by ammonia water, separating precipitate, washing the precipitate with water until no chloride ions exist, and drying;
2) Soaking the precipitate in the step 1) by sulfuric acid solution, taking out, drying and roasting to obtain the steel slag-based zirconium catalyst.
14. The method according to claim 13, wherein in step 1), the soluble zirconium salt is selected from any one or a combination of at least two of zirconium oxychloride, zirconium chloride anhydrous, zirconium nitrate pentahydrate;
the soluble salt of the rare earth element is selected from any one or a combination of at least two of hydrochloride and nitrate;
the concentration of the soluble zirconium salt dissolved in water is 0.001-0.2 g/mL; the concentration of the soluble salt of the rare earth element dissolved in water is 0.0014-0.01 g/mL;
the mass ratio of the soluble zirconium salt in the impregnating solution to the steel slag is 1:2.5 to 3;
the dipping time is 0.5-5 h;
the concentration of the ammonia water is 10-25 wt%;
the drying temperature is 100-120 ℃ and the drying time is 4-6 h.
15. The method of claim 14, wherein the soluble salt of a rare earth element is selected from lanthanum chloride or cerium chloride.
16. The method of claim 14, wherein the soluble zirconium salt is dissolved in water at a concentration of 0.01 to 0.1g/mL; the concentration of the soluble salt of the rare earth element dissolved in water is 0.0022-0.0070 g/mL.
17. The preparation method according to claim 14, wherein the mass ratio of the soluble zirconium salt in the impregnating solution to the steel slag is 1:2.6 to 2.7.
18. The method of claim 14, wherein the immersion time is 1 to 2 hours.
19. The method according to claim 14, wherein the ammonia concentration is 15 to 20wt%.
20. The preparation method according to claim 13, wherein in the step 2), the mass ratio of the precipitate to the sulfuric acid solution is 1:5-15 when the precipitate is immersed in the sulfuric acid solution;
the concentration of the sulfuric acid solution is 0.1-4 mol/L, and the sulfuric acid solution is an aqueous solution of sulfuric acid;
the soaking time is 1-3 h;
the drying is carried out at the temperature of 100-120 ℃ for 4-6 hours;
the roasting temperature is 500-700 ℃ and the time is 2-4 h.
21. The method according to claim 20, wherein the mass ratio of the precipitate to the sulfuric acid solution is 1:8-10.
22. The method according to claim 20, wherein the sulfuric acid solution has a concentration of 1 to 2mol/L.
23. The method of claim 20, wherein the firing temperature is 575 to 625 ℃ for a time period of 2.5 to 3.5 hours.
24. Use of the steel slag based zirconium catalyst of any one of claims 1-12 or the steel slag based zirconium catalyst prepared by the method of any one of claims 13-23 for catalyzing the selective dehydration reaction of 2-methyl-3-hydroxy-1-propanal.
25. A process for preparing 1, 4-butanediol with the co-production of methacrolein, characterized in that it employs the steel slag-based zirconium catalyst according to any one of claims 1 to 12 or the steel slag-based zirconium catalyst prepared by the process according to any one of claims 13 to 23, comprising the steps of:
(1) The aqueous solution containing 4-hydroxy butyraldehyde and 2-methyl-3-hydroxy-1-propionaldehyde enters a reaction extraction tower filled with the steel slag-based zirconium catalyst, the 2-methyl-3-hydroxy-1-propionaldehyde is converted into isoolefine butyraldehyde through dehydration reaction, meanwhile, an organic extractant is added, the isoolefine butyraldehyde is obtained through extraction phase separation, and the aqueous solution containing 4-hydroxy butyraldehyde and unreacted 2-methyl-3-hydroxy-1-propionaldehyde is obtained from a raffinate phase;
(2) And (3) carrying out hydrogenation reaction on the raffinate phase obtained in the step (1) to convert 4-hydroxybutyraldehyde into 1, 4-butanediol.
26. The method of claim 25, wherein in step (1), the aqueous solution comprising 4-hydroxybutyraldehyde, 2-methyl-3-hydroxy-1-propanal, comprises: 10 to 20 weight percent of 4-hydroxy butyraldehyde, 1 to 2 weight percent of 2-methyl-3-hydroxy-1-propionaldehyde, 0.01 to 0.02 weight percent of propionaldehyde and the balance of water;
The treatment amount of the steel slag-based zirconium catalyst is 1-10 g of aqueous solution containing 4-hydroxy butyraldehyde and 2-methyl-3-hydroxy-1-propanal/(g of catalyst. H);
the dehydration reaction is carried out at the reaction temperature of 70-150 ℃ and the reaction pressure of normal pressure or micro-positive pressure;
the theoretical plate number of the reaction extraction tower is 5-10;
the organic extractant is water-insoluble organic matter and is one or more selected from aromatic hydrocarbon compounds, aliphatic hydrocarbon compounds and ether compounds;
the mass ratio of the organic extractant to the aqueous solution containing 4-hydroxybutyraldehyde and 2-methyl-3-hydroxy-1-propanal is 1:1-10.
27. The method according to claim 26, wherein the steel slag-based zirconium catalyst has a treatment amount of 2 to 5g of an aqueous solution containing 4-hydroxybutyraldehyde and 2-methyl-3-hydroxy-1-propanal/(g of catalyst. H).
28. The method of claim 26, wherein the dehydration reaction is performed at a temperature of 100 to 120 ℃ and a reaction pressure of 0 to 0.1mpa g.
29. The method of claim 26, wherein the organic extractant is selected from one or more of toluene, xylene, cyclohexane, heptane, diethyl ether, butyl ether.
30. The method according to claim 26, wherein the mass ratio of the organic extractant to the aqueous solution containing 4-hydroxybutyraldehyde and 2-methyl-3-hydroxy-1-propanal is 1:4-6.
31. The method according to claim 25, wherein in the step (2), the hydrogenation reaction is carried out at a temperature of 125 to 135 ℃, a reaction pressure of 3 to 8MPa and a reaction time of 0.5 to 2 hours, and a crude hydrogenation reaction solution is obtained after the reaction is completed.
32. The process of claim 25, wherein in step (2), the hydrogenation reaction is carried out under catalytic conditions using a raney nickel catalyst.
33. The method according to claim 32, wherein the catalyst is used in an amount of 1 to 5% by mass of the aqueous solution containing 4-hydroxybutyraldehyde and unreacted 2-methyl-3-hydroxy-1-propanal.
34. The method according to claim 33, wherein the catalyst is used in an amount of 2 to 3% by mass of the aqueous solution containing 4-hydroxybutyraldehyde and unreacted 2-methyl-3-hydroxy-1-propanal.
35. The method of claim 25, wherein steps (1) and (2) further comprise a separation operation after the reaction is completed to obtain a high purity methacrolein, 1, 4-butanediol product.
36. The method according to claim 35, wherein the extract phase in the step (1) is separated by normal pressure rectification to obtain methacrolein, the number of plates of the rectification column is 8-10 in the normal pressure rectification process, the methacrolein product is obtained by collecting the fraction at 68.5-69.5 ℃, the organic extractant is obtained by collecting the fraction at 110-111 ℃, and the separated organic extractant can be returned to the reaction extraction column in the step (1) for recycling.
37. The method according to claim 35, wherein the crude hydrogenation reaction liquid obtained by the hydrogenation reaction in the step (2) is separated by vacuum distillation to obtain 1, 4-butanediol, wherein the number of plates of a distillation column is 20 to 25 during the vacuum distillation, low boiling point compounds are firstly separated by collecting fractions with a pressure of 5 to 20Kpa and a temperature of 30 to 80 ℃, and then the 1, 4-butanediol product is obtained by collecting fractions with a pressure of 1.9 to 2.1Kpa and a temperature of 124 to 126 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111313106.3A CN114160116B (en) | 2021-11-08 | 2021-11-08 | Zirconium catalyst based on steel slag, preparation method and application thereof in preparation of 1, 4-butanediol and co-production of methacrolein |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111313106.3A CN114160116B (en) | 2021-11-08 | 2021-11-08 | Zirconium catalyst based on steel slag, preparation method and application thereof in preparation of 1, 4-butanediol and co-production of methacrolein |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114160116A CN114160116A (en) | 2022-03-11 |
| CN114160116B true CN114160116B (en) | 2023-05-30 |
Family
ID=80478167
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111313106.3A Active CN114160116B (en) | 2021-11-08 | 2021-11-08 | Zirconium catalyst based on steel slag, preparation method and application thereof in preparation of 1, 4-butanediol and co-production of methacrolein |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114160116B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114849679B (en) * | 2022-04-01 | 2024-02-02 | 万华化学集团股份有限公司 | Solid super acid supported catalyst and preparation method of beta-phenethyl alcohol |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108940235A (en) * | 2018-07-25 | 2018-12-07 | 广西大学 | The in-situ precipitate preparation method and application of geo-polymer defluorinating agent |
| CN109107525A (en) * | 2018-09-25 | 2019-01-01 | 中国环境科学研究院 | More metal zeroth order mercury absorbents of a kind of converter slag containing vanadium and titanium oxides load and preparation method thereof |
| CN109422624A (en) * | 2017-09-05 | 2019-03-05 | 东营市海科新源化工有限责任公司 | A kind of preparation method of 1,3 butylene glycol |
| CN112456638A (en) * | 2020-09-29 | 2021-03-09 | 江苏环保产业技术研究院股份公司 | Modified steel slag filler and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113165897A (en) * | 2018-10-10 | 2021-07-23 | 里克希维亚有限公司 | Compositions and methods for purifying metals from steelmaking waste streams |
-
2021
- 2021-11-08 CN CN202111313106.3A patent/CN114160116B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109422624A (en) * | 2017-09-05 | 2019-03-05 | 东营市海科新源化工有限责任公司 | A kind of preparation method of 1,3 butylene glycol |
| CN108940235A (en) * | 2018-07-25 | 2018-12-07 | 广西大学 | The in-situ precipitate preparation method and application of geo-polymer defluorinating agent |
| CN109107525A (en) * | 2018-09-25 | 2019-01-01 | 中国环境科学研究院 | More metal zeroth order mercury absorbents of a kind of converter slag containing vanadium and titanium oxides load and preparation method thereof |
| CN112456638A (en) * | 2020-09-29 | 2021-03-09 | 江苏环保产业技术研究院股份公司 | Modified steel slag filler and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114160116A (en) | 2022-03-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108236955B (en) | Preparation method of catalyst for synthesizing ethanol by dimethyl oxalate hydrogenation, catalyst obtained by preparation method and application of catalyst | |
| EP3015448B1 (en) | Method for producing acrylic acid from glycerol | |
| CN107930647B (en) | Catalyst, preparation method thereof and preparation method of 2-ethylhexanal | |
| CN101544539A (en) | Method for producing polymer grade ethylene glycol and co-producing methyl glycolate | |
| CN102105429A (en) | Method for producing (meth)acrylic acid anhydride, method for storing (meth)acrylic acid anhydride, and method for producing (meth)acrylate ester | |
| CN114160116B (en) | Zirconium catalyst based on steel slag, preparation method and application thereof in preparation of 1, 4-butanediol and co-production of methacrolein | |
| CN103044367B (en) | Production method of gamma-butyrolactone | |
| CN101759530A (en) | Method for preparing hydroquinone | |
| CN1289753A (en) | Process for preparing ketone by dehydrogenating para-alcohol | |
| CN109438216B (en) | Preparation method of high-purity isooctanoic acid | |
| CN114425367B (en) | Catalyst system for preparing acrylic ester by carbonylation of acetylene, preparation and application thereof | |
| CN103360220A (en) | Method for producing more hydroquinone | |
| CN112387268A (en) | Solid base catalyst for preparing 3-hydroxybutyraldehyde and preparation method thereof | |
| CN114849679B (en) | Solid super acid supported catalyst and preparation method of beta-phenethyl alcohol | |
| CN109867589B (en) | Preparation method of propylene glycol monoalkyl ether | |
| CN107445839A (en) | The synthetic method of glyoxylic ester | |
| CN107445832A (en) | The method of ethyl glycolate oxidation generation glyoxylic ester | |
| CN114773188B (en) | Continuous recovery method of methyl cardiac acid raffinate | |
| CN101993363A (en) | Method for preparing oxalic ester by CO coupling | |
| CN105152938B (en) | A kind of technique efficiently synthesizing secondary carbon primary amine N1923 | |
| CN109851588A (en) | The refining methd of propylene oxide | |
| CN116328825B (en) | Catalyst, preparation method thereof and method for preparing methyl 3-methoxypropionate by using catalyst to catalyze methanol and methyl acetate | |
| CN103889967A (en) | Method for producing cis-rose oxide | |
| CN109534954B (en) | Method and device for coproducing cyclohexanol and ethanol | |
| CN114832782B (en) | Deoxidizing adsorbent for Fischer-Tropsch light distillate oil adsorption-rectification coupling technology and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |