CN112279824A - Dehydrogenation reaction system - Google Patents
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- CN112279824A CN112279824A CN202011202479.9A CN202011202479A CN112279824A CN 112279824 A CN112279824 A CN 112279824A CN 202011202479 A CN202011202479 A CN 202011202479A CN 112279824 A CN112279824 A CN 112279824A
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- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract
The invention discloses a dehydrogenation reaction system, which is used for preparing gamma-butyrolactone and comprises the following steps: a. premixing: 1, 4-butanediol and hydrogen respectively enter a vaporizer to be mixed, and then enter a superheater to obtain a hot raw material; b. dehydrogenation: b, enabling the hot raw material in the step a to enter a dehydrogenation reaction bed, and obtaining a reactant under the action of a catalyst; c. heat exchange: b, enabling the reactant in the step b to pass through a heat exchanger to obtain a crude product; d. condensation: c, enabling the crude product in the step c to enter a subsequent working section, condensing gamma-butyrolactone in the crude product to obtain a final product, and collecting the final product; the hydrogen in the crude product is returned to the vaporizer via a heat exchanger. The system recycles hydrogen in the system, reduces the gasification condition of 1, 4-butanediol, greatly improves the reaction rate, reduces the heat load of a dehydrogenation reaction bed, can also be used for cooling products by heat exchange of recycle hydrogen, and simultaneously raises the temperature of the hydrogen, so that the production process further saves a large amount of energy and reduces the production cost.
Description
Technical Field
The invention relates to the technical field of chemical production, in particular to a dehydrogenation reaction system.
Background
Gamma-butyrolactone is a colorless oily liquid, can be dissolved in water, dissolved in methanol, ethanol, acetone, ether and benzene, can be volatilized with water vapor, and can be decomposed in hot alkaline solution. The gamma-butyrolactone has wide application, can be used as a high-boiling-point solvent, has strong solubility, good electrical property and stability and is safe to use; can be used as proton type strong solvent to dissolve most of low molecular polymer and part of high molecular polymer; can be used as battery electrolyte to replace strong corrosive acid liquid; can be used as a carrier in the polymerization reaction and participate in the polymerization reaction; can be used for preparing pyrrolidone, butyric acid, succinic acid, paint remover, etc.; the method has wide application in the synthesis of fine chemicals such as medicines, spices and the like; in the polyurethane field, it is useful as a viscosity modifier for polyurethanes, and as a curing agent for polyurethane and amino coating systems. The method for synthesizing gamma-butyrolactone comprises a furfural method, a maleic anhydride hydrogenation method, a succinic acid hydrogenation method and a butanediol dehydrogenation method, wherein the butanediol dehydrogenation method has mature technology and simple flow and is widely used in the field.
The method for preparing gamma-butyrolactone by dehydrogenation of 1, 4-butanediol can generate a large amount of byproduct hydrogen, the byproduct hydrogen is treated by a methanation process and then sent to other hydrogenation processes for use, or is directly discharged, and the utilization rate of the byproduct is low; moreover, because the dehydrogenation reaction is an endothermic reaction, a large amount of energy is consumed in the production process; in addition, the reaction rate can be increased by the 1, 4-butanediol being reacted in a gaseous state, but it is difficult for the existing production equipment to achieve gasification conditions.
Disclosure of Invention
In order to solve the above problems, the present invention provides a dehydrogenation reaction system for preparing gamma-butyrolactone, comprising the steps of:
a. premixing: 1, 4-butanediol and hydrogen respectively enter a vaporizer to be mixed, and then enter a superheater to obtain a hot raw material;
b. dehydrogenation: b, enabling the hot raw material in the step a to enter a dehydrogenation reaction bed, and obtaining a reactant under the action of a catalyst;
c. heat exchange: b, enabling the reactant in the step b to pass through a heat exchanger to obtain a crude product;
d. condensation: c, enabling the crude product in the step c to enter a subsequent working section, condensing gamma-butyrolactone in the crude product to obtain a final product, and collecting the final product; the hydrogen in the crude product is returned to the vaporizer via a heat exchanger.
As a preferable technical scheme, the temperature in the vaporizer is 150-200 ℃, and the gauge pressure is 0.04-0.08 MPa.
As a preferable technical scheme, the temperature in the vaporizer is 160-180 ℃, and the gauge pressure is 0.05-0.07 MPa.
As a preferable technical scheme, the flow rate of the hydrogen entering the vaporizer is 40-60 square/min.
As a preferable technical scheme, the temperature in the superheater is 200-250 ℃, and the gauge pressure is 0.04-0.08 MPa.
As a preferable technical scheme, the temperature in the superheater is 220-230 ℃, and the gauge pressure is 0.05-0.07 MPa.
As a preferable technical scheme, the reaction temperature in the dehydrogenation reaction bed is 200-250 ℃.
As a preferable technical scheme, the reaction temperature in the dehydrogenation reaction bed is 210-230 ℃.
As a preferred technical solution, the heat exchanger includes a first heat exchanger and a second heat exchanger.
As a preferable technical scheme, the temperature of the hydrogen in the crude product is 30-50 ℃.
Has the advantages that: the invention provides a dehydrogenation reaction system, which is used for producing gamma-butyrolactone, hydrogen is recycled in the system, the gasification condition of 1, 4-butanediol is reduced, the reaction rate is greatly improved, the heat load of a dehydrogenation reaction bed is reduced, the recycle hydrogen can be used for cooling products through heat exchange, and the temperature of the hydrogen is increased, so that the production process further saves a large amount of energy and reduces the production cost.
Drawings
To further illustrate the benefits of a dehydrogenation reaction system provided herein, the accompanying drawings are provided, and it is noted that the drawings provided herein are merely selected examples of all drawings, and are not intended as limitations on the claims, and that all other corresponding figures obtained from the drawings provided herein are to be considered within the scope of protection of the present application.
FIG. 1 is a schematic diagram of a dehydrogenation reaction system according to the present invention.
Reference numerals: 1-vaporizer, 2-superheater, 3-dehydrogenation reaction bed, 4-first heat exchanger, 5-second heat exchanger and 6-subsequent working section.
Detailed Description
The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
The term "prepared from …" as used herein is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
Approximating language, as used herein throughout the specification and claims, is intended to modify a quantity, such that the invention is not limited to the specific quantity, but includes portions that are literally received for modification without substantial change in the basic function to which the invention is related. Accordingly, the use of "about" to modify a numerical value means that the invention is not limited to the precise value. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.
In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.
The present invention is described below by way of specific embodiments, but is not limited to the specific embodiments given below.
In order to solve the problems in the prior art, the invention provides a dehydrogenation reaction system for preparing gamma-butyrolactone, which comprises the following steps:
a. premixing: respectively feeding 1, 4-Butanediol (BDO) and hydrogen into a vaporizer for mixing, and then feeding into a superheater to obtain a hot raw material;
b. dehydrogenation: b, enabling the hot raw material in the step a to enter a dehydrogenation reaction bed, and obtaining a reactant under the action of a catalyst;
c. heat exchange: b, enabling the reactant in the step b to pass through a heat exchanger to obtain a crude product;
d. condensation: c, enabling the crude product in the step c to enter a subsequent working section, condensing gamma-butyrolactone (GBL) in the crude product to obtain a final product, and collecting the final product; the hydrogen in the crude product is returned to the vaporizer via a heat exchanger.
From the viewpoint of balancing energy consumption and reaction rate, in some preferred embodiments, the temperature in the vaporizer is 150 to 200 ℃ and the gauge pressure is 0.04 to 0.08 MPa; further preferably, the temperature in the vaporizer is 160-180 ℃, and the gauge pressure is 0.05-0.06 MPa.
The gauge pressure in the present invention refers to a fluid indicated pressure based on atmospheric pressure, and is measured by a pressure gauge, i.e., absolute pressure-atmospheric pressure.
In some preferred embodiments, the flow rate of the hydrogen gas into the vaporizer is 40 to 60 square/min; further preferably, the flow rate of the hydrogen entering the vaporizer is 45-55 square/min.
The flow of hydrogen into the vaporizer in the present invention can be controlled by any method known to those skilled in the art, using a method of pressurizing the gas using a blower. The unit of the flow in the invention is square/min, which is called as cubic meter/min, and is a unit of gas flow, and the unit represents the volume of gas passing through every minute at 0 ℃ and 1 standard atmospheric pressure. The invention adjusts the hydrogen partial pressure in the vaporizer by controlling the flow of the hydrogen.
The reaction rate of the dehydrogenation reaction can be obviously increased by feeding the 1, 4-butanediol in a gaseous state, however, the boiling point of the 1, 4-butanediol at normal pressure is 228 ℃, and the boiling point of the 1, 4-butanediol also rises at the absolute pressure of 1.6bar of the system, so that the requirement on equipment is higher, and the energy consumption is greatly increased. The inventor finds that the dehydrogenation reaction after mixing 1, 4-butanediol with hydrogen can greatly improve the reaction efficiency because the partial pressure of the hydrogen can vaporize a large amount of 1, 4-butanediol, the hydrogen can be used as a heat carrier, the stability of the reaction temperature is ensured, the heat load of a dehydrogenation reaction bed is reduced, the uniform dispersion of the 1, 4-butanediol on a catalyst can be improved, the catalytic efficiency is improved, and the surface of the catalyst can be swept to play a role in activating the catalyst. However, the inventor also found that, because the dehydrogenation reaction generates hydrogen, the addition of hydrogen is not favorable for the forward direction of the reaction from the viewpoint of reaction thermodynamics, so the hydrogen partial pressure needs to be strictly controlled, when the hydrogen partial pressure is too high, the reaction rate of the dehydrogenation reaction is slow due to too high concentration of the product, the conversion rate of 1, 4-butanediol is reduced, the yield of gamma-butyrolactone is reduced, the dehydrogenation reaction proceeds slowly, but a side reaction is promoted, so that the number of by-products is increased; when the hydrogen partial pressure is too low, the vaporization of 1, 4-butanediol is insufficient, the contact of the catalyst with reactants is reduced, and the catalyst is easy to inactivate, thus the production requirement can not be met.
In some preferred embodiments, the temperature in the superheater is 200 to 250 ℃, and the gauge pressure is 0.04 to 0.08 MPa; more preferably, the temperature in the superheater is 220-230 ℃, and the gauge pressure is 0.05-0.07 MPa.
The catalyst for dehydrogenation in the present invention is not particularly limited and may be any one known to those skilled in the art, and a metal oxide such as Cr is generally used2O3-Al2O3、Fe2O3-Cr2O3-K2O、Ca8Ni(PO4)6-Cr2O3And the like.
In some preferred embodiments, the reaction temperature in the dehydrogenation reaction bed is 200 to 250 ℃; further preferably, the reaction temperature in the dehydrogenation reaction bed is 210-230 ℃.
The dehydrogenation reaction is an endothermic reaction, the higher the reaction temperature is, the forward reaction is facilitated, the conversion rate of 1, 4-butanediol is increased, however, the heating increases the energy consumption on one hand, and on the other hand, the side reactions such as dehydration of 1, 4-butanediol into tetrahydrofuran or hydrogenation into 1-butanol are also aggravated, which leads to the increase of reaction byproducts. The inventor finds that the reaction can be rapidly carried out and the yield of the gamma-butyrolactone is high when the reaction temperature is controlled within 200-250 ℃ in long-term research, and side reactions can be reduced, so that the purity of the circulating hydrogen is ensured, and the production can be continuously carried out.
In some preferred embodiments, the heat exchanger comprises a first heat exchanger and a second heat exchanger for gas-gas heat exchange between the reaction product and the recycle hydrogen.
In some preferred embodiments, the temperature of the hydrogen in the crude product is from 30 to 50 ℃.
The temperature of the hydrogen in the crude product in the present invention can be adjusted by controlling the temperature of the condensing equipment in the subsequent section.
After the crude product enters a subsequent working section, gamma-butyrolactone in the crude product is condensed and collected to obtain a product, hydrogen carried in the crude product is cooled, the crude product firstly passes through the heat exchanger when returning to the system, cold hydrogen and reactants in the heat exchanger generate heat exchange, the temperature of the reactants is reduced, the condensation time in the subsequent working section is shortened, the temperature of the cold hydrogen is increased, the energy consumption required by reheating the hydrogen is saved, and the cold hydrogen can directly return to the vaporizer for recycling. The inventor finds that when the temperature of hydrogen in the crude product is 30-50 ℃, not only the energy consumption of the system is greatly reduced, but also the continuous production is ensured, and the reason is that a small amount of byproducts in the crude product can be condensed and completely separated from the hydrogen at lower temperature, so that the purity of the circulating hydrogen is improved, the byproducts can be discharged out of the system, the byproducts in the reaction can not be continuously enriched along with the production, however, the load of a cooling system can be increased when the temperature is too low, and the energy consumption of the system is not reduced and increased.
Examples
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
Example 1
Example 1 provides a dehydrogenation reaction system for preparing gamma-butyrolactone, as shown in fig. 1, comprising the following steps:
a. premixing: 1, 4-butanediol and hydrogen respectively enter a vaporizer 1 to be mixed, and then enter a superheater 2 to obtain hot raw materials; the temperature in the vaporizer 1 is 160 ℃, and the gauge pressure is 0.06 MPa; the flow rate of the hydrogen entering the vaporizer 1 is 50 square/min; the temperature in the superheater 2 is 220 ℃, and the gauge pressure is 0.06 MPa;
b. dehydrogenation: the hot material in the step a enters a dehydrogenation reaction bed 3 and is in the presence of a catalyst Cr2O3-Al2O3Obtaining a reactant under the action of the catalyst; the reaction temperature in the dehydrogenation reaction bed is 230 ℃;
c. heat exchange: b, enabling the reactant in the step b to pass through a first heat exchanger 4 and a second heat exchanger 5 to obtain a crude product;
d. condensation: c, the crude product in the step c enters a subsequent working section 6, gamma-butyrolactone in the crude product is condensed to obtain a final product, and the final product is collected; the temperature of hydrogen in the crude product is 40 ℃, and the hydrogen returns to the vaporizer 1 after passing through the second heat exchanger 5 and the first heat exchanger 4 in sequence.
Example 2
Example 2 provides a dehydrogenation reaction system for preparing gamma-butyrolactone, as shown in fig. 1, comprising the following steps:
a. premixing: 1, 4-butanediol and hydrogen respectively enter a vaporizer 1 to be mixed, and then enter a superheater 2 to obtain hot raw materials; the temperature in the vaporizer 1 is 160 ℃, and the gauge pressure is 0.06 MPa; the flow rate of the hydrogen entering the vaporizer 1 is 50 square/min; the temperature in the superheater 2 is 220 ℃, and the gauge pressure is 0.06 MPa;
b. dehydrogenation: b, enabling the hot raw material in the step a to enter a dehydrogenation reaction bed 3, and obtaining a reactant under the action of a catalyst Cr2O3-Al2O 3; the reaction temperature in the dehydrogenation reaction bed was 280 ℃;
c. heat exchange: b, enabling the reactant in the step b to pass through a first heat exchanger 4 and a second heat exchanger 5 to obtain a crude product;
d. condensation: c, the crude product in the step c enters a subsequent working section 6, gamma-butyrolactone in the crude product is condensed to obtain a final product, and the final product is collected; the temperature of hydrogen in the crude product is 40 ℃, and the hydrogen returns to the vaporizer 1 after passing through the second heat exchanger 5 and the first heat exchanger 4 in sequence.
Example 3
Example 3 provides a dehydrogenation reaction system for preparing gamma-butyrolactone, as shown in fig. 1, comprising the following steps:
a. premixing: 1, 4-butanediol and hydrogen respectively enter a vaporizer 1 to be mixed, and then enter a superheater 2 to obtain hot raw materials; the temperature in the vaporizer 1 is 160 ℃, and the gauge pressure is 0.06 MPa; the flow rate of the hydrogen entering the vaporizer 1 is 50 square/min; the temperature in the superheater 2 is 220 ℃, and the gauge pressure is 0.06 MPa;
b. dehydrogenation: b, enabling the hot raw material in the step a to enter a dehydrogenation reaction bed 3, and obtaining a reactant under the action of a catalyst Cr2O3-Al2O 3; the reaction temperature in the dehydrogenation reaction bed is 200 ℃;
c. heat exchange: b, enabling the reactant in the step b to pass through a first heat exchanger 4 and a second heat exchanger 5 to obtain a crude product;
d. condensation: c, the crude product in the step c enters a subsequent working section 6, gamma-butyrolactone in the crude product is condensed to obtain a final product, and the final product is collected; the temperature of hydrogen in the crude product is 40 ℃, and the hydrogen returns to the vaporizer 1 after passing through the second heat exchanger 5 and the first heat exchanger 4 in sequence.
Example 4
Example 4 provides a dehydrogenation reaction system for preparing gamma-butyrolactone, as shown in fig. 1, comprising the following steps:
a. premixing: 1, 4-butanediol and hydrogen respectively enter a vaporizer 1 to be mixed, and then enter a superheater 2 to obtain hot raw materials; the temperature in the vaporizer 1 is 160 ℃, and the gauge pressure is 0.06 MPa; the flow rate of the hydrogen entering the vaporizer 1 is 50 square/min; the temperature in the superheater 2 is 220 ℃, and the gauge pressure is 0.06 MPa;
b. dehydrogenation: b, enabling the hot raw material in the step a to enter a dehydrogenation reaction bed 3, and obtaining a reactant under the action of a catalyst Cr2O3-Al2O 3; the reaction temperature in the dehydrogenation reaction bed is 230 ℃;
c. heat exchange: b, enabling the reactant in the step b to pass through a first heat exchanger 4 and a second heat exchanger 5 to obtain a crude product;
d. condensation: c, the crude product in the step c enters a subsequent working section 6, gamma-butyrolactone in the crude product is condensed to obtain a final product, and the final product is collected; the temperature of hydrogen in the crude product is 70 ℃, and the hydrogen returns to the vaporizer 1 after sequentially passing through the second heat exchanger 5 and the first heat exchanger 4.
Example 5
Example 5 provides a dehydrogenation reaction system for preparing gamma-butyrolactone, as shown in fig. 1, comprising the following steps:
a. premixing: 1, 4-butanediol and hydrogen respectively enter a vaporizer 1 to be mixed, and then enter a superheater 2 to obtain hot raw materials; the temperature in the vaporizer 1 is 160 ℃, and the gauge pressure is 0.06 MPa; the flow rate of the hydrogen entering the vaporizer 1 is 50 square/min; the temperature in the superheater 2 is 220 ℃, and the gauge pressure is 0.06 MPa;
b. dehydrogenation: b, enabling the hot raw material in the step a to enter a dehydrogenation reaction bed 3, and obtaining a reactant under the action of a catalyst Cr2O3-Al2O 3; the reaction temperature in the dehydrogenation reaction bed is 230 ℃;
c. heat exchange: b, enabling the reactant in the step b to pass through a first heat exchanger 4 and a second heat exchanger 5 to obtain a crude product;
d. condensation: c, the crude product in the step c enters a subsequent working section 6, gamma-butyrolactone in the crude product is condensed to obtain a final product, and the final product is collected; the temperature of hydrogen in the crude product is 20 ℃, and the hydrogen returns to the vaporizer 1 after passing through the second heat exchanger 5 and the first heat exchanger 4 in sequence.
Example 6
Example 6 provides a dehydrogenation reaction system for preparing gamma-butyrolactone, as shown in fig. 1, comprising the following steps:
a. premixing: 1, 4-butanediol and hydrogen respectively enter a vaporizer 1 to be mixed, and then enter a superheater 2 to obtain hot raw materials; the temperature in the vaporizer 1 is 160 ℃, and the gauge pressure is 0.06 MPa; the flow rate of the hydrogen entering the vaporizer 1 is 80 square/min; the temperature in the superheater 2 is 220 ℃, and the gauge pressure is 0.06 MPa;
b. dehydrogenation: b, enabling the hot raw material in the step a to enter a dehydrogenation reaction bed 3, and obtaining a reactant under the action of a catalyst Cr2O3-Al2O 3; the reaction temperature in the dehydrogenation reaction bed is 230 ℃;
c. heat exchange: b, enabling the reactant in the step b to pass through a first heat exchanger 4 and a second heat exchanger 5 to obtain a crude product;
d. condensation: c, the crude product in the step c enters a subsequent working section 6, gamma-butyrolactone in the crude product is condensed to obtain a final product, and the final product is collected; the temperature of hydrogen in the crude product is 40 ℃, and the hydrogen returns to the vaporizer 1 after passing through the second heat exchanger 5 and the first heat exchanger 4 in sequence.
Example 7
Example 7 provides a dehydrogenation reaction system for preparing gamma-butyrolactone, as shown in fig. 1, comprising the following steps:
a. premixing: 1, 4-butanediol and hydrogen respectively enter a vaporizer 1 to be mixed, and then enter a superheater 2 to obtain hot raw materials; the temperature in the vaporizer 1 is 160 ℃, and the gauge pressure is 0.06 MPa; the flow rate of the hydrogen entering the vaporizer 1 is 30 square/min; the temperature in the superheater 2 is 220 ℃, and the gauge pressure is 0.06 MPa;
b. dehydrogenation: b, enabling the hot raw material in the step a to enter a dehydrogenation reaction bed 3, and obtaining a reactant under the action of a catalyst Cr2O3-Al2O 3; the reaction temperature in the dehydrogenation reaction bed is 230 ℃;
c. heat exchange: b, enabling the reactant in the step b to pass through a first heat exchanger 4 and a second heat exchanger 5 to obtain a crude product;
d. condensation: c, the crude product in the step c enters a subsequent working section 6, gamma-butyrolactone in the crude product is condensed to obtain a final product, and the final product is collected; the temperature of hydrogen in the crude product is 40 ℃, and the hydrogen returns to the vaporizer 1 after passing through the second heat exchanger 5 and the first heat exchanger 4 in sequence.
Evaluation of Performance
The final products obtained in examples 1 to 7 were measured by high performance liquid chromatography, and the test contents included the conversion rate of 1, 4-butanediol and the yield of γ -butyrolactone in the products produced after the system continuously produced for 6 hours and 24 hours, where the conversion rate of 1, 4-butanediol was equal to the mass percentage of 1, 4-butanediol in 1-final product, and the yield of γ -butyrolactone was the mass percentage of γ -butyrolactone in the final product, and the results are shown in table 1.
TABLE 1
According to the embodiment, the dehydrogenation reaction system provided by the invention can be used for continuous production, the high conversion rate of 1, 4-butanediol is ensured, and the yield of gamma-butyrolactone is improved, in addition, the embodiment 1 of the invention can save energy by more than 30% after being put into practical use, and is suitable for being widely popularized in the industry.
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is the intention of the inventors that the appended claims not be limited by the choice of examples illustrating the features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (10)
1. A dehydrogenation reaction system for producing gamma-butyrolactone, comprising the steps of:
a. premixing: 1, 4-butanediol and hydrogen respectively enter a vaporizer to be mixed, and then enter a superheater to obtain a hot raw material;
b. dehydrogenation: b, enabling the hot raw material in the step a to enter a dehydrogenation reaction bed, and obtaining a reactant under the action of a catalyst;
c. heat exchange: b, enabling the reactant in the step b to pass through a heat exchanger to obtain a crude product;
d. condensation: c, enabling the crude product in the step c to enter a subsequent working section, condensing gamma-butyrolactone in the crude product to obtain a final product, and collecting the final product; the hydrogen in the crude product is returned to the vaporizer via a heat exchanger.
2. The dehydrogenation reaction system of claim 1, wherein the vaporizer has a temperature of 150 to 200 ℃ and a gauge pressure of 0.04 to 0.08 MPa.
3. The dehydrogenation reaction system of claim 2, wherein the temperature in the vaporizer is from 160 to 180 ℃ and the gauge pressure is from 0.05 to 0.07 MPa.
4. The dehydrogenation reaction system of claim 1, wherein the hydrogen gas is introduced into the vaporizer at a flow rate of 40 to 60 square/min.
5. The dehydrogenation reaction system according to claim 1, wherein the temperature in the superheater is 200 to 250 ℃ and the gauge pressure is 0.04 to 0.08 MPa.
6. The dehydrogenation reaction system according to claim 5, wherein the temperature in the superheater is 220 to 230 ℃ and the gauge pressure is 0.05 to 0.06 MPa.
7. The dehydrogenation reaction system of claim 1, wherein the reaction temperature in the dehydrogenation reaction bed is in the range of from 200 ℃ to 250 ℃.
8. The dehydrogenation reaction system of claim 7, wherein the reaction temperature in the dehydrogenation reaction bed is in the range of from 210 ℃ to 230 ℃.
9. The dehydrogenation reaction system of claim 1, wherein the heat exchanger comprises a first heat exchanger and a second heat exchanger.
10. The dehydrogenation reaction system of any one of claims 1-9, wherein the temperature of the hydrogen gas in the crude product is from 30 ℃ to 50 ℃.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013076747A1 (en) * | 2011-11-25 | 2013-05-30 | Conser Spa | Process for producing 1,4- butanediol by hydrogenating dialkyl maleate in mixed liquid/vapor phase |
| CN203768274U (en) * | 2014-04-01 | 2014-08-13 | 垦利县东垦更新化工厂 | System for one-time production of gamma-butyrolactone through dehydrogenation and catalytic distillation of 1,4-butanediol |
| CN211688878U (en) * | 2020-02-29 | 2020-10-16 | 山东长信化学科技股份有限公司 | Dehydrogenation reaction system with good energy-saving effect |
| CN211688877U (en) * | 2020-02-27 | 2020-10-16 | 山东长信化学科技股份有限公司 | Dehydrogenation reaction system that reaction efficiency is high |
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2020
- 2020-11-02 CN CN202011202479.9A patent/CN112279824A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013076747A1 (en) * | 2011-11-25 | 2013-05-30 | Conser Spa | Process for producing 1,4- butanediol by hydrogenating dialkyl maleate in mixed liquid/vapor phase |
| CN203768274U (en) * | 2014-04-01 | 2014-08-13 | 垦利县东垦更新化工厂 | System for one-time production of gamma-butyrolactone through dehydrogenation and catalytic distillation of 1,4-butanediol |
| CN211688877U (en) * | 2020-02-27 | 2020-10-16 | 山东长信化学科技股份有限公司 | Dehydrogenation reaction system that reaction efficiency is high |
| CN211688878U (en) * | 2020-02-29 | 2020-10-16 | 山东长信化学科技股份有限公司 | Dehydrogenation reaction system with good energy-saving effect |
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