CN114409504B - Method for preparing 1, 4-butanediol by hydrogenating 1, 4-butynediol - Google Patents

Method for preparing 1, 4-butanediol by hydrogenating 1, 4-butynediol Download PDF

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CN114409504B
CN114409504B CN202210045285.5A CN202210045285A CN114409504B CN 114409504 B CN114409504 B CN 114409504B CN 202210045285 A CN202210045285 A CN 202210045285A CN 114409504 B CN114409504 B CN 114409504B
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butanediol
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pressure
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赵永祥
刘绍波
李海涛
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Shanxi University
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    • 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
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • C07C29/172—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with the obtention of a fully saturated alcohol
    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • 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
    • B01J25/00—Catalysts of the Raney type
    • B01J25/02—Raney nickel
    • 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
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
    • 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
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Abstract

The invention relates to a method for preparing 1, 4-butanediol by hydrogenating 1, 4-butynediol, wherein a pressurized 1, 4-butynediol aqueous solution enters a low-pressure reactor, a hydrogenation reaction product in the first step enters a normal-pressure cyclone separator after being depressurized, a reaction liquid is extracted from the top of the separator, and catalyst particles are further removed from the reaction liquid through a bag filter; the reaction liquid enters a pre-separation tower, the reaction liquid is cut in a vacuum state, water, n-butyl alcohol and light components are distilled out from the top of the tower, and a mixed aqueous solution containing 1, 4-butanediol, 1, 4-butylene glycol, hydroxybutanal, acetal and heavy components is discharged from the bottom of the tower; the mixed aqueous solution is preheated by a pressurizing and high-pressure hydrogenation preheater and then enters a chilled water heat-removing tubular reactor, the mixed aqueous solution is converted into 1, 4-butanediol under the action of a catalyst, reactants are extracted from the bottom of the reactor, and then the 1, 4-butanediol product is obtained after distillation, and the purpose of reducing energy consumption is achieved by separating and changing the form of the hydrogenation reactor in advance.

Description

Method for preparing 1, 4-butanediol by hydrogenating 1, 4-butynediol
Technical Field
The invention relates to a method for producing 1, 4-butanediol, in particular to a method for preparing 1, 4-butanediol by hydrogenating 1, 4-butynediol.
Background
1, 4-butanediol (BDO for short) is an important organic and fine chemical raw material, and is widely applied to the fields of medicine, chemical industry, textile, papermaking, automobiles, daily chemical industry and the like. Tetrahydrofuran (THF), polybutylene terephthalate (PBT), gamma-butyl lactone (GBL), polyurethane Resin (PU Resin), paint, plasticizer, etc. can be produced from 1, 4-butanediol, and as a solvent, a brightening agent for the electroplating industry, etc.
Before the second world war, lei Peifa was used in germany to synthesize 1, 4-butanediol from acetylene and formaldehyde. The method solves the danger of acetylene operation under high pressure, and is still the most main production method of 1, 4-butanediol. In the 60 s, mitsubishi oil company of japan developed a process for preparing 1, 4-butanediol by catalytic hydrogenation of maleic anhydride, and in the 70 s, developed a new process for the acetoxylation of butadiene. In 1971, the industrial company of Toyoda, japan established a production facility for the butadiene chlorination process. In addition, various synthesis methods using propylene or ethylene as a raw material have been studied successively in the united states and japan.
The Lei Pei method has the advantages of less complex production process and lower cost. The production capacity of the method is close to 90% of the total capacity of various methods, and the key of the development of the method in the future is the supply and price of acetylene raw materials.
The maleic anhydride hydrogenation process has two steps and co-production of tetrahydrofuran. The method has high raw material price, but has few reaction steps, low investment and adjustable obtained byproducts, so that many countries are still under the tight research and development.
1, 4-Dichlorobutene Process 1, 4-Dichlorobutene is an intermediate in the production of chloroprene from butadiene. The Toyo-Cao industry developed a process in which 1, 4-dichlorobutene is hydrolyzed with an excess of sodium formate at about 110 ℃ to produce 2-butene-1, 4-diol at a conversion of nearly 100% and a selectivity of greater than 90%. After hydrolysis, the free formic acid is neutralized with sodium hydroxide. Then 2-butene-1, 4-diol is hydrogenated to obtain 1, 4-butanediol at 100 deg.C and 27MPa in the presence of nickel-aluminium catalyst. The method has high public engineering cost and high production cost.
China has rich coal resources. Compared with other production processes, the raw materials of Lei Peifa are mainly supplied for coal post-processing. Therefore, lei Peifa is of more practical significance in the production of 1, 4-butanediol in China.
The synthesis of the first step 1, 4-butynediol in the existing Lei Pei method production process is basically consistent, and the use modes of the catalysts are slightly different. The difference is large in the hydrogenation section, the first process is that the whole system is high-pressure fixed bed hydrogenation, and high-flow 30-40 wt%1, 4-butynediol aqueous solution is adopted for cyclic hydrogenation; the other process is a two-stage method, wherein the addition product is subjected to low-pressure hydrogenation and then subjected to high-pressure hydrogenation to be thoroughly converted; compared with the two methods, the second method saves the energy consumption of the hydrogenation section under the condition of ensuring the conversion rate and the product quality;
the traditional two-step hydrogenation process for preparing 1, 4-butanediol comprises the following steps: the first step (also called one-stage hydrogenation) generally adopts a suspension bed (or bubbling slurry bed), uses Raney-nickel catalyst, carries out low-pressure hydrogenation under the hydrogen pressure of 1-3 MPa at 50-80 ℃, hydrogenates 30-40 wt% of 1, 4-butynediol aqueous solution into 1, 4-butanediol aqueous solution, and contains n-butanol, unsaturated hydrogenation products of 1, 4-butylene glycol, acetals and other high-boiling substances and low-boiling substances obtained by condensation reaction of 4-hydroxybutanal and aldehyde of 1, 4-butylene glycol isomerization products and alcohol; because 4-hydroxybutanal, acetal and 1, 4-butylene glycol cannot be removed by a rectification method, the purity and quality of the product are affected in the product, and further high-pressure hydrogenation removal is needed; and in the second step (two-stage hydrogenation), the product solution of the first stage is hydrogenated at the reaction temperature of 110-160 ℃ and the hydrogen pressure of 12-21 MPa by adopting a fixed bed reactor and taking supported nickel as a catalyst, and mainly relates to the further hydroconversion of a small amount of 1, 4-butylene glycol, an isomerised product hydroxybutanal and acetal in the material so as to improve the yield of the 1, 4-butanediol and reduce the existence of impurities.
The above process has been disclosed many times in the prior art, but because of the heat removal requirement of the traditional fixed bed trickle reaction system in the second stage hydrogenation process, the hydrogenation process with low concentration and large flow is still adopted, and a large amount of water (60-70 wt%) exists in the system, so that the energy consumption of the system is increased.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for preparing 1, 4-butanediol by hydrogenating 1, 4-butynediol, which achieves the purpose of reducing energy consumption by separating in advance.
In order to solve the technical problems, the invention adopts the following technical scheme: a method for preparing 1, 4-butanediol by hydrogenating 1, 4-butynediol comprises the following steps:
step one, a pressurized 30-40 wt%1, 4-butynediol aqueous solution enters a low-pressure reactor, a first-step hydrogenation reaction is carried out under the action of a Raney nickel-aluminum-X catalyst, a product enters a normal-pressure cyclone separator after being depressurized, the Raney nickel-aluminum-X catalyst is separated from the bottom of the separator, a reaction liquid is extracted from the top, and catalyst particles are further removed from the reaction liquid through a bag filter;
step two, the reaction liquid enters a pre-separation tower; cutting the reaction liquid under vacuum, distilling water, n-butanol and light components from the top of the tower, and obtaining a mixed aqueous solution containing 1, 4-butanediol, 1, 4-butylene glycol, hydroxybutanal, acetal and heavy components from the bottom of the tower;
thirdly, water, n-butanol and light components separated from the top of the pre-separation tower enter a next separation section to extract byproduct n-butanol;
and fourthly, preheating the mixed aqueous solution separated from the bottom of the pre-separation tower through a pressurizing and high-pressure hydrogenation preheater, then entering a chilled water heat removal tubular reactor, converting 1, 4-butylene glycol, hydroxybutanal and acetal into 1, 4-butanediol under the action of a catalyst, extracting reactants from the bottom of the reactor, and distilling to obtain a 1, 4-butanediol product.
Further, in the first step, the Raney nickel-aluminum-X catalyst used in the low-pressure reactor consists of the following components in percentage by mass of nickel to aluminum (0.5-1): 1. the addition amount of X is 1-2 wt% of the total mass of nickel-aluminum, and the metal powder is obtained after 25% NaOH treatment; wherein X is any one of Mg, B, sr, cr, S, ti, la, sn, W, mo, fe. Preferably, X is Mg.
Further, in the first step, the inlet solution of the low-pressure reactor is a 30-40 wt%1, 4-butynediol aqueous solution, the inlet temperature is 40-45 ℃, the inlet pressure is 1.1-4.1 MPa, and the liquid airspeed is 1-4 h -1 The method comprises the steps of carrying out a first treatment on the surface of the The inlet gas is 99.99wt% hydrogen, the inlet pressure is 1.1-4.1 MPa, and the gas space velocity is 11-1.5 h -1 The method comprises the steps of carrying out a first treatment on the surface of the The outlet pressure of the liquid is 0.4-0.8 MPa, and the outlet temperature is 60-75 ℃.
Further, the low pressure reactor is a slurry bed reactor with a jacketed heat removal system.
Further, in the second step, the theoretical plate number of the pre-separation tower is 3-5, and the operating pressure is 15 KPa-25 KPa; the operating temperature is 60-75 ℃.
In the fourth step, the high-pressure hydrogenation preheater is a shell-and-tube heat exchanger, the liquid inlet temperature is 60-75 ℃, and the liquid outlet temperature is 95-140 ℃.
Further, in the fourth step, the composition of the catalyst filled in the chilled water heat removal tube reactor is as follows: the nickel content is 11-22 wt%, the accelerator content is 1-6wt%, the rest is alumina, and the accelerator is one of lanthanum, copper and magnesium elements.
Further, the chilled water heat removal tubular reactor R is a tubular reactor, the catalyst is filled in the tubular reactor, the shell side is subjected to chilled water heat removal, and the reaction temperature is controlled at 95-140 ℃; the reaction pressure is controlled to be 10.0-30.0 MPa, and the space velocity of the reactor liquid is 0.5-2.5 h -1 。
Further, the catalyst separated from the bag filter and the catalyst separated from the bottom of the cyclone were circulated to the low pressure reactor to take part in the reaction again.
In the invention, the inventor grasps the reaction rules of low-pressure 1, 4-butynediol hydrogenation and high-pressure hydrogenation reaction through catalyst comparison test, activity evaluation, theoretical calculation and software simulation, screens out a reasonable reaction form of a catalyst suitable for medium-pressure 1, 4-butynediol hydrogenation and a high-pressure hydrogenation catalyst under high concentration, solves the problem of high energy consumption in the existing two-stage 1, 4-butynediol hydrogenation process, and achieves the purposes of completing the process target and reducing the energy consumption by separating and changing the hydrogenation reactor form in advance.
In particular, compared with the prior art, the invention has the following advantages:
(1) The outlet temperature of the low-pressure reactor in the prior art is 60-75 ℃, and materials containing about 60% of water, butanol and other components are heated to 95-140 ℃ before high-pressure hydrogenation, so that a large amount of energy is consumed. According to the invention, under the condition of no heating, the solution after low-pressure hydrogenation is separated in advance, and about 60 weight percent of the weight of the reaction solution is removed before high-pressure hydrogenation, so that the energy consumption of a high-pressure hydrogenation section is greatly reduced. Meanwhile, the material handling capacity of the high-pressure hydrogenation section is correspondingly reduced, and the size of the whole high-pressure pressurizing equipment is reduced and the investment is greatly reduced when the 1, 4-butanediol handling capacity is the same.
(2) The concentration of the high-pressure materials, the increase of the concentration of the reactants not only requires higher catalyst activity, but also aggravates the exothermic reaction, and the higher requirements for the heat removal of the reactor are provided. The prior art high pressure reaction adopts common Ni/Al 2 O 3 The catalyst has low activity and can not meet the activity requirement of high-concentration reaction materials. The adopted fixed bed tower reactor has low heat removal efficiency, and can easily cause the temperature runaway of the catalyst bed layer, so that the catalyst is irreversibly deactivated. In one aspect of the invention, a novel high-efficiency hydrogenation catalyst which is newly developed is adopted, the nickel content of the catalyst is 11-22 wt%, the accelerator content is 1-6 wt%, the rest is aluminum oxide, and the accelerator is one of lanthanum, copper and magnesium elements. The active component nickel of the catalyst is introduced into the carrier in a mode of impregnating the catalyst by mixed salt solution, the mixed nickel salt is formed by mixing inorganic nickel salt and organic nickel salt, and the active component can be promoted to be uniformly deposited on the inner surface of the catalyst carrier due to the synergic and competitive adsorption effects between anions, so that a high-dispersion catalyst product is obtained. Meanwhile, a proper amount of surfactant polyethylene glycol or CTAB is added into the impregnating solution, so that on one hand, the solubility is increased, on the other hand, the dispersion of nickel species is further promoted, carbon deposition generated in the roasting process can prevent the active components from agglomerating, and meanwhile, the interaction between the active components and the carrier is regulated. Due to the adoption of a special catalyst preparation method, the obtained catalyst keeps high dispersity under higher active component loading, and has proper surface acidity and alkalinity, proper pore structure and proper interaction between metal and a carrier. Thus exhibiting high catalytic activity and selectivity in high hydrogenation and having a long catalyst life.
(3) Aiming at the problem of aggravation of heat release of high-concentration materials, the type of the traditional high-pressure hydrogenation reactor is optimized, and the original simple fixed bed tower reactor is changed into a high-pressure tubular reactor with better heat removal effect, so that the reaction heat is smoothly removed in the process of high-concentration reaction.
The 1, 4-butanediol product with the purity of more than or equal to 99.5% and the chromaticity of less than or equal to 10AHPA can be obtained after the process flow. The consumption of public engineering is greatly reduced, the power consumption is lower than 420 kilowatt-hours/ton of 1, 4-butanediol, the steam consumption is lower than 4.5 tons/ton of 1, 4-butanediol, and the circulating cooling water consumption is lower than 320 tons/ton of 1, 4-butanediol.
Drawings
FIG. 1 is a flow chart of the prior art for the hydrogenation of 1, 4-butynediol to 1, 4-butanediol.
FIG. 2 is a flow chart of the hydrogenation of 1, 4-butynediol to 1, 4-butanediol according to the present invention.
Detailed Description
The following examples are provided to further illustrate the claimed invention. However, examples and comparative examples are provided for the purpose of illustrating embodiments of the present invention and do not exceed the scope of the inventive subject matter, which is not limited by the examples.
In the following examples, reference is made to patent document CN 102744083A for a preparation method of raney nickel-aluminum-X catalyst. The preparation method of the catalyst loaded in the chilled water heat removal tube reactor can be referred to in patent document publication No. CN 101306368A.
Unless specifically indicated otherwise, materials and reagents used in the present invention are available from commercial products in the art.
Example 1
In this example, the Raney nickel-aluminum-X catalyst used in the low pressure reactor R1 consists of: the mass ratio of nickel to aluminum is 0.5: the addition amount of X is 1wt% of the total mass of nickel aluminum, wherein X is Mg. The preparation process is as follows: respectively weighing 250kg of Ni blocks, 500kg of Al blocks and 7.5kg of Mg in a medium-large furnace, turning on current, after Ni, al and Mg are melted, carrying out heat preservation and smelting at 900 ℃ for 60min, and pouring into water for cooling; grinding the catalyst obtained after cooling to 200 meshes of powder; weighing a proper amount of catalyst powder in batches, adding the catalyst powder into a 25% NaOH solution in batches, uniformly mixing, then controlling the temperature to be 60 ℃ for reaction for 30min, washing the catalyst powder with distilled water for 3 times after the reaction is finished, and washing the catalyst powder with absolute ethyl alcohol until the catalyst powder is neutral.
Catalyst filled in the chilled water heat removal tubular reactor R2 comprises the following components: nickel 11-wt%, accelerator Mg 1-wt% and alumina the rest. The catalyst was prepared as follows. The specific surface is 220 m 2 ·g -1 Pore volume of 0.7. 0.7 cm 3 ·g -1 The alumina carrier 88 Kg with the average pore diameter of 12 nm is prepared by taking 10.6 Kg magnesium nitrate hexahydrate to prepare 100L solution, soaking the solution into the alumina carrier, standing for 30min, drying at 120 ℃ for 12 h, and roasting at 500 ℃ for 6 h to obtain the carrier containing the accelerator Mg. Vacuum-pumping the above carrier at 150deg.C for 10 min, and cooling to room temperature for use. Weighing 29.7 Kg nickel nitrate hexahydrate, 21.3 Kg nickel nitrate tetrahydrate and 2 Kg polyethylene glycol, preparing into 100L solution, soaking on the carrier containing the accelerator Mg, standing for 20 min, and filtering to remove the residual solution; drying at 80 deg.c to 10 h deg.c, roasting at 250 deg.c to 10 h deg.c, introducing hydrogen gas at 450 deg.c to reduce to 5h, and deactivating the reduced catalyst with oxygen gas for use.
(1) The aqueous solution of 1,4 butynediol with the weight percent of 30 percent and the temperature of 40 ℃ is pressurized to 4.1MPa and enters a low-pressure reactor R1, the reaction pressure is kept to be controlled at 4.1MPa, the reaction temperature is kept at 60 ℃, and the space velocity of the reaction liquid is regulated to be 1h -1 Hydrogen (99.99%) was added at a pressure of 4.1MPa and a gas space velocity of 1.5h -1 Carrying out first-step hydrogenation; the product is decompressed to 0.4MPa and enters a cyclone separator S1; the Raney nickel-aluminum-X catalyst separated from the bottom of the cyclone separator S1 is extracted from the top, and the reaction liquid is further removed by a bag filter S2; the catalyst separated from the bag filter S2 and the catalyst separated from the bottom of the cyclone S1 are circulated to the low-pressure reactor R1 to participate in the reaction again;
(2) The reaction solution treated as described above was fed into the pre-separation column T1, the number of theoretical plates was 5, and the operation temperature was maintained at 75℃at 15 KPa. The reaction liquid is cut, water, butanol and light components are distilled out from the top of the tower, and a mixed aqueous solution of 1, 4-butanediol, 1, 4-butylene glycol, hydroxybutanal and acetal and heavy components is discharged from the bottom of the tower;
(3) The water, butanol and light components separated from the top of the pre-separation tower T1 enter the next separation section to extract byproduct butanol;
(4) The mixed aqueous solution separated from the bottom of the pre-separation tower T1 is preheated by a pressurizing and high-pressure hydrogenation preheater E1 and then heated to 120 ℃, the pressure is increased to 20MPa, the mixed aqueous solution enters a chilled water heat removal tubular reactor R2 from the top in a trickling mode, and the reaction temperature is controlled at 140 ℃; the reaction pressure is controlled at 20MPa and the airspeed is 0.5h -1 The method comprises the steps of carrying out a first treatment on the surface of the Further, a small amount of 1, 4-butylene glycol, hydroxybutanal and acetal are converted into 1, 4-butanediol, and the reactant is withdrawn from the bottom of the reactor R2. And then the 1, 4-butanediol product with the purity of 99.6% and the chromaticity of 5AHPA is obtained after distillation. The power electricity consumption is 400 kilowatt-hours/ton of 1, 4-butanediol, the steam consumption is 4.1 tons/ton of 1, 4-butanediol, and the circulating cooling water consumption is 300 tons/ton of 1, 4-butanediol.
Comparative example 1
In this example, the same Raney nickel-aluminum-X catalyst as in example 1 was used in the low pressure reactor, and the high pressure hydrogenation catalyst had a nickel content of 11% wt%, a promoter Mg content of 1% wt% and the balance alumina. The existing hydrogenation process is adopted:
(1) The aqueous solution of 1,4 butynediol with the weight percent of 30 percent and the temperature of 40 ℃ is pressurized to 4.1MPa and enters a low-pressure hydrogenation reactor, the reaction pressure is kept to be controlled to be 4.1MPa, the reaction temperature is kept to be 60 ℃, and the space velocity of the reaction liquid is regulated to be 1h -1 Hydrogen (99.99%) was added at a pressure of 4.1MPa and a gas space velocity of 1.5h -1 Carrying out first-step hydrogenation; the product is decompressed to 0.4MPa and enters a separator, and the separated catalyst is circulated to a low-pressure reactor to participate in the reaction again;
(2) Preheating the separated materials by a pressurizing and high-pressure hydrogenation preheater, heating to 120 ℃, boosting to 20MPa, enabling the materials to enter a fixed bed reactor from the top in a trickling mode, and controlling the reaction temperature at 140 ℃; the reaction pressure is controlled at 20MPa and the airspeed is 0.5h -1 The method comprises the steps of carrying out a first treatment on the surface of the Further, a small amount of 1, 4-butylene glycol, hydroxybutanal and acetal are converted into 1, 4-butanediol, and the reactants are taken out from the bottom of the reactor. Then distilled to obtain the product with the purity of 99.5 percent, chromaticity and the like1, 4-butanediol product at 5 AHPA. The power electricity consumes 485 kilowatt hours per ton of 1, 4-butanediol, the steam consumes 5.3 tons per ton of 1, 4-butanediol, and the circulating cooling water consumes 353 tons per ton of 1, 4-butanediol.
Example 2
In this example, the Raney nickel-aluminum-X catalyst used in the low pressure reactor R1 consists of: the mass ratio of nickel to aluminum is 0.6: the addition amount of X is 1wt% of the total mass of nickel aluminum, wherein X is Mg. The preparation process is as follows: respectively weighing 300kg of Ni blocks, 500kg of Al blocks and 8kg of Mg in a medium-large furnace, turning on current, after Ni, al and Mg are melted, carrying out heat preservation and smelting at 900 ℃ for 60min, and pouring into water for cooling; grinding the catalyst obtained after cooling to 200 meshes of powder; weighing a proper amount of catalyst powder in batches, adding the catalyst powder into a 25% NaOH solution in batches, uniformly mixing, then controlling the temperature to be 60 ℃ for reaction for 30min, washing the catalyst powder with distilled water for 3 times after the reaction is finished, and washing the catalyst powder with absolute ethyl alcohol until the catalyst powder is neutral.
Catalyst filled in the chilled water heat removal tubular reactor R2 comprises the following components: nickel 13-wt%, promoter La 3-wt% and alumina the rest. The catalyst is prepared by the following steps: the specific surface is 300 m 2 ·g -1 Pore volume of 1.1 cm 3 ·g -1 Taking 9.4 Kg lanthanum nitrate hexahydrate from an alumina carrier 84 Kg with an average pore diameter of 17 nm, preparing into a 120L solution, soaking the solution into the alumina carrier, standing for 20 min, drying at 110 ℃ for 10 h, and roasting at 400 ℃ for 6 h to obtain the carrier containing the accelerator La. Drying the carrier at 150 ℃ for 10 h, and cooling to room temperature for standby. Weighing 39.6 Kg nickel nitrate hexahydrate, 17.0 Kg nickel nitrate tetrahydrate and 3Kg CTAB, preparing into 120L solution, soaking the solution on the carrier containing the accelerator La, standing for 30min, and filtering out the residual solution; drying at 100deg.C for 8 h, calcining at 450deg.C for 6 h, introducing hydrogen gas at 400deg.C for 5h, and protecting the reduced catalyst with liquid.
(1) The aqueous solution of 1,4 butynediol with the weight percent of 35 percent and the temperature of 40 ℃ is pressurized to 3.0MPa and enters a low-pressure reactor R1, the reaction pressure is kept to be 3.0MPa, the reaction temperature is kept to be 60 ℃, and the space velocity of the reaction liquid is regulatedFor 2h -1 The pressure of the added hydrogen (99.99%) is 3MPa, and the gas space velocity is 3h -1 Carrying out first-step hydrogenation; the product is decompressed to 0.4MPa and enters a cyclone separator S1; the Raney nickel-aluminum-X catalyst is separated from the bottom of the cyclone separator S1, the reaction liquid is extracted from the top, and the reaction liquid is further removed by the bag filter S2; the catalyst separated from the bag filter S2 and the catalyst separated from the bottom of the cyclone S1 are circulated to the low-pressure reactor R1 to participate in the reaction again;
(2) The reaction liquid treated by the method enters a pre-separation tower T1, and the theoretical plate number is 4; at 20KPa, the operating temperature was maintained at 70 ℃. The reaction solution is cut, water, butanol and light components are distilled out from the top of the tower, and heavy components, 1, 4-butanediol, 1, 4-butylene glycol, hydroxybutanal and acetal aqueous solution are discharged from the bottom of the tower;
(3) The water, butanol and light components separated from the top of the pre-separation tower T1 enter the next separation section to extract byproduct butanol;
(4) The solution separated from the bottom of the pre-separation tower T1 is preheated by a pressurizing and high-pressure hydrogenation preheater E1 and then heated to 120 ℃, the temperature is increased to 25MPa, and the solution enters a chilled water heat-removing tubular reactor R2 from the top in a trickling mode, and the reaction temperature is controlled at 130 ℃; the reaction pressure is controlled at 25MPa, and the airspeed is 1.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the Further, a small amount of 1, 4-butylene glycol, hydroxybutanal and acetal are converted into 1, 4-butanediol, and the reactant is withdrawn from the bottom of the reactor R2. And then the 1, 4-butanediol product with the purity of 99.7 percent and the chromaticity of 3AHPA is obtained after distillation. The power electricity consumption is 400 kilowatt-hours/ton of 1, 4-butanediol, the steam consumption is 4.1 tons/ton of 1, 4-butanediol, and the circulating cooling water consumption is 300 tons/ton of 1, 4-butanediol.
Example 3
In this example, the Raney nickel-aluminum-X catalyst used in the low pressure reactor R1 consists of: the mass ratio of nickel to aluminum is 0.7: the addition amount of X is 1wt% of the total mass of nickel aluminum, wherein X is Mg. The manufacturing process is as follows: respectively weighing 350kg of Ni blocks, 500kg of Al blocks and 8.5kg of Mg in a medium-large furnace, turning on current, after Ni, al and Mg are melted, carrying out heat preservation and smelting at 900 ℃ for 60min, and pouring into water for cooling; grinding the catalyst obtained after cooling to 200 meshes of powder; weighing a proper amount of catalyst powder in batches, adding the catalyst powder into a 25% NaOH solution in batches, uniformly mixing, then controlling the temperature to be 60 ℃ for reaction for 30min, washing the catalyst powder with distilled water for 3 times after the reaction is finished, and washing the catalyst powder with absolute ethyl alcohol until the catalyst powder is neutral;
catalyst filled in the chilled water heat removal tubular reactor R2 comprises the following components: nickel content 19 wt%, promoter Cu content 5wt%, and the balance alumina. The catalyst is prepared by the following steps: the specific surface is 150 m 2 ·g -1 Pore volume of 1.3 cm 3 ·g -1 The alumina carrier 76 Kg with the average pore diameter of 20 nm is prepared by preparing a solution of 100L from 19.0 Kg copper nitrate trihydrate, soaking the solution into the alumina carrier, standing for 30min, drying at 110 ℃ for 10 h, and roasting at 400 ℃ for 6 h to obtain the carrier containing the accelerator Cu. Drying the carrier at 150 ℃ for 10 h, and cooling to room temperature for standby. Weighing 49.5 Kg nickel nitrate hexahydrate, 38.1 Kg nickel nitrate tetrahydrate and 2 Kg CTAB, preparing 130L solution, dipping the solution on the carrier containing the accelerator Cu, standing for 30min, and filtering out the residual solution; drying at 100deg.C for 8 h, calcining at 450deg.C for 6 h, introducing hydrogen gas at 400deg.C for 5h, and protecting the reduced catalyst with liquid.
(1) The 1, 4-butynediol aqueous solution with the weight percent of 35 percent and the temperature of 40 ℃ is pressurized to 2.5MPa and enters a low-pressure reactor R1, the reaction pressure is kept to be controlled at 2.5MPa, the reaction temperature is kept at 60 ℃, and the space velocity of the reaction liquid is regulated to be 3h -1 Hydrogen (99.99%) was added at a pressure of 2.5MPa and a gas space velocity of 4. 4h -1 Carrying out first-step hydrogenation; the product is decompressed to 0.4MPa and enters a cyclone separator S1; the Raney-nickel catalyst separated from the bottom of the cyclone separator S1 is extracted from the top, and the reaction liquid is further removed by a bag filter S2; the catalyst separated from the bag filter S2 and the catalyst separated from the bottom of the cyclone S1 are circulated to the low-pressure reactor R1 to participate in the reaction again;
(2) The reaction liquid treated by the method enters a pre-separation tower T1, and the theoretical plate number is 4; at 20KPa, the operating temperature was maintained at 70 ℃. The reaction solution is cut, water, butanol and light components are distilled out from the top of the tower, and heavy components, 1, 4-butanediol, 1, 4-butylene glycol, hydroxybutanal and acetal aqueous solution are discharged from the bottom of the tower;
(3) The water, butanol and light components separated from the top of the pre-separation tower T1 enter the next separation section to extract byproduct butanol;
(4) The solution separated from the bottom of the pre-separation tower T1 is preheated by a pressurizing and high-pressure hydrogenation preheater E1 and then heated to 110 ℃, the temperature is increased to 25MPa, and the solution enters a chilled water heat-removing tubular reactor R2 from the top in a trickling mode, and the reaction temperature is controlled at 120 ℃; the reaction pressure is controlled at 25MPa, and the airspeed is 1.5h -1 The method comprises the steps of carrying out a first treatment on the surface of the Further, a small amount of 1, 4-butylene glycol, hydroxybutanal and acetal are converted into 1, 4-butanediol, and the reactants are taken out from the bottom of the reactor. And then the 1, 4-butanediol product with the purity of 99.6 percent and the chromaticity of 3AHPA is obtained after distillation. The power electricity consumes 395 kilowatt-hours per ton of 1, 4-butanediol, the steam consumes 4.0 tons per ton of 1, 4-butanediol, and the circulating cooling water consumes 295 tons per ton of 1, 4-butanediol.
Example 4
In this example, the Raney nickel-aluminum-X catalyst used in the low pressure reactor R1 consists of: the mass ratio of nickel to aluminum is 0.8: the addition amount of X is 1wt% of the total mass of nickel aluminum, wherein X is Mg. The manufacturing process is as follows: respectively weighing 400kg of Ni blocks, 500kg of Al blocks and 9kg of Mg in a medium-large furnace, turning on current, after Ni, al and Mg are melted, carrying out heat preservation and smelting at 900 ℃ for 60min, and pouring into water for cooling; grinding the catalyst obtained after cooling to 200 meshes of powder; weighing a proper amount of catalyst powder in batches, adding the catalyst powder into a 25% NaOH solution in batches, uniformly mixing, then controlling the temperature to be 60 ℃ for reaction for 30min, washing the catalyst powder with distilled water for 3 times after the reaction is finished, and washing the catalyst powder with absolute ethyl alcohol until the catalyst powder is neutral;
catalyst filled in the chilled water heat removal tubular reactor R2 comprises the following components: nickel content 22 wt%, promoter Cu content 6 wt%, and the rest is alumina. The catalyst is prepared by the following steps: the specific surface is 150 m 2 ·g -1 Pore volume of 1.3 cm 3 ·g -1 Average pore diameter of 20The method comprises the steps of preparing a 100L solution from 22.8 Kg copper nitrate trihydrate, immersing the solution into an alumina carrier 72 Kg with nm alumina carrier, standing for 30min, drying at 110 ℃ for 10 h, and roasting at 400 ℃ for 6 h to obtain the carrier containing the accelerator Cu. Drying the carrier at 150 ℃ for 10 h, and cooling to room temperature for standby. Weighing 74.3 Kg nickel nitrate hexahydrate, 29.7 Kg nickel nitrate tetrahydrate and 2 Kg CTAB, preparing 130L solution, dipping the solution on the carrier containing the accelerator Cu, standing for 30min, and filtering out the residual solution; drying at 100deg.C for 8 h, calcining at 450deg.C for 6 h, introducing hydrogen gas at 400deg.C for 5h, and protecting the reduced catalyst with liquid.
(1) The 40wt percent 1, 4-butynediol aqueous solution which is pressurized to 2.0MPa and is at 40 ℃ enters a low pressure reactor R1, the reaction pressure is kept to be controlled at 2.0MPa, the reaction temperature is kept at 60 ℃, and the space velocity of the reaction liquid is regulated to be 4h -1 Hydrogen (99.99%) was added at a pressure of 2.0MPa and a gas space velocity of 2h -1 Carrying out first-step hydrogenation; the product is decompressed to 0.4MPa and enters a cyclone separator S1; the Raney-nickel catalyst separated from the bottom of the cyclone separator S1 is extracted from the top, and the reaction liquid is further removed by a bag filter S2; the catalyst separated from the bag filter S2 and the catalyst separated from the bottom of the cyclone S1 are circulated to the low-pressure reactor R1 to participate in the reaction again;
(2) The reaction liquid treated by the method enters a pre-separation tower T1, and the theoretical plate number is 5; at 15KPa, the operating temperature was maintained at 75deg.C. The reaction solution is cut, water, butanol and light components are distilled out from the top of the tower, and heavy components, 1, 4-butanediol, 1, 4-butylene glycol, hydroxybutanal and acetal aqueous solution are discharged from the bottom of the tower;
(3) The water, butanol and light components separated from the top of the pre-separation tower T1 enter the next separation section to extract byproduct butanol;
(4) The solution separated from the bottom of the pre-separation tower T1 is preheated by a pressurizing and high-pressure hydrogenation preheater E1 and then heated to 120 ℃, the temperature is increased to 25MPa, and the solution enters a chilled water heat-removing tubular reactor R2 from the top in a trickling mode, and the reaction temperature is controlled at 130 ℃; the reaction pressure is controlled at 25MPa, and the airspeed is 1.5h -1 The method comprises the steps of carrying out a first treatment on the surface of the Further, a small amount of 1, 4-butylene glycol, hydroxybutanal and acetal are converted into 1, 4-butanediol, and the reaction product is withdrawn from the bottom R2 of the reactor. And then the 1, 4-butanediol product with the purity of 99.7 percent and the chromaticity of 2AHPA is obtained after distillation. The power electricity consumption is 400 kilowatt-hours/ton of 1, 4-butanediol, the steam consumption is 4.1 tons/ton of 1, 4-butanediol, and the circulating cooling water consumption is 300 tons/ton of 1, 4-butanediol.
Example 5
In this example, the Raney nickel-aluminum-X catalyst used in the low pressure reactor R1 consists of: the mass ratio of nickel to aluminum is 1: the addition amount of X is 2wt% of the total mass of nickel aluminum, wherein X is Mg. The manufacturing process is as follows: respectively weighing 400kg of Ni blocks, 500kg of Al blocks and 9kg of Mg in a medium-large furnace, turning on current, after Ni, al and Mg are melted, carrying out heat preservation and smelting at 900 ℃ for 60min, and pouring into water for cooling; grinding the catalyst obtained after cooling to 200 meshes of powder; weighing a proper amount of catalyst powder in batches, adding the catalyst powder into a 25% NaOH solution in batches, uniformly mixing, then controlling the temperature to be 60 ℃ for reaction for 30min, washing the catalyst powder with distilled water for 3 times after the reaction is finished, and washing the catalyst powder with absolute ethyl alcohol until the catalyst powder is neutral;
catalyst filled in the chilled water heat removal tubular reactor R2 comprises the following components: nickel content 22 wt%, promoter Cu content 6 wt%, and the rest is alumina. The catalyst is prepared by the following steps: the specific surface is 150 m 2 ·g -1 Pore volume of 1.3 cm 3 ·g -1 The alumina carrier 72 Kg with the average pore diameter of 20 nm is prepared by preparing a solution of 100L from 22.8 Kg copper nitrate trihydrate, soaking the solution into the alumina carrier, standing for 30min, drying at 110 ℃ for 10 h, and roasting at 400 ℃ for 6 h to obtain the carrier containing the accelerator Cu. Drying the carrier at 150 ℃ for 10 h, and cooling to room temperature for standby. Weighing 74.3 Kg nickel nitrate hexahydrate, 29.7 Kg nickel nitrate tetrahydrate and 2 Kg CTAB, preparing 130L solution, dipping the solution on the carrier containing the accelerator Cu, standing for 30min, and filtering out the residual solution; drying at 100deg.C for 8 h, calcining at 450deg.C for 6 h, introducing hydrogen gas at 400deg.C for 5h, and protecting the reduced catalyst with liquid.
(1) The 40wt percent 1, 4-butynediol aqueous solution which is pressurized to 1.1MPa and is at 45 ℃ enters a low pressure reactor R1, the reaction pressure is kept to be controlled at 1.1MPa, the reaction temperature is kept at 75 ℃, and the space velocity of the reaction liquid is regulated to be 4h -1 Hydrogen (99.99%) was added at a pressure of 1.1MPa and a gas space velocity of 1.5h -1 Carrying out first-step hydrogenation; the product is decompressed to 0.8MPa and enters a cyclone separator S1; the Raney-nickel catalyst separated from the bottom of the cyclone separator S1 is extracted from the top, and the reaction liquid is further removed by a bag filter S2; the catalyst separated from the bag filter S2 and the catalyst separated from the bottom of the cyclone S1 are circulated to the low-pressure reactor R1 to participate in the reaction again;
(2) The reaction liquid treated by the method enters a pre-separation tower T1, and the theoretical plate number is 3; at 25KPa, the operating temperature was maintained at 60 ℃. The reaction solution is cut, water, butanol and light components are distilled out from the top of the tower, and heavy components, 1, 4-butanediol, 1, 4-butylene glycol, hydroxybutanal and acetal aqueous solution are discharged from the bottom of the tower;
(3) The water, butanol and light components separated from the top of the pre-separation tower T1 enter the next separation section to extract byproduct butanol;
(4) The solution separated from the bottom of the pre-separation tower T1 is preheated by a pressurizing and high-pressure hydrogenation preheater E1 and then heated to 95 ℃, the temperature is increased to 10MPa, and the solution enters a chilled water heat-removing tubular reactor R2 from the top in a trickling mode, and the reaction temperature is controlled at 95 ℃; the reaction pressure is controlled to be 10MPa, and the airspeed is controlled to be 2.5h -1 The method comprises the steps of carrying out a first treatment on the surface of the Further, a small amount of 1, 4-butylene glycol, hydroxybutanal and acetal are converted into 1, 4-butanediol, and the reaction product is withdrawn from the bottom R2 of the reactor. And then the 1, 4-butanediol product with the purity of 99.7 percent and the chromaticity of 2AHPA is obtained after distillation. The power electricity consumes 380 kilowatt-hours per ton of 1, 4-butanediol, the steam consumes 3.8 tons per ton of 1, 4-butanediol, and the circulating cooling water consumes 290 tons per ton of 1, 4-butanediol.
Example 6
In this example, the Raney nickel-aluminum-X catalyst used in the low pressure reactor R1 consists of: the mass ratio of nickel to aluminum is 0.8: the addition amount of X is 1wt% of the total mass of nickel aluminum, wherein X is Mg. The manufacturing process is as follows: respectively weighing 400kg of Ni blocks, 500kg of Al blocks and 9kg of Mg in a medium-large furnace, turning on current, after Ni, al and Mg are melted, carrying out heat preservation and smelting at 900 ℃ for 60min, and pouring into water for cooling; grinding the catalyst obtained after cooling to 200 meshes of powder; weighing a proper amount of catalyst powder in batches, adding the catalyst powder into a 25% NaOH solution in batches, uniformly mixing, then controlling the temperature to be 60 ℃ for reaction for 30min, washing the catalyst powder with distilled water for 3 times after the reaction is finished, and washing the catalyst powder with absolute ethyl alcohol until the catalyst powder is neutral;
catalyst filled in the chilled water heat removal tubular reactor R2 comprises the following components: nickel content 22 wt%, promoter Cu content 6 wt%, and the rest is alumina. The catalyst is prepared by the following steps: the specific surface is 150 m 2 ·g -1 Pore volume of 1.3 cm 3 ·g -1 The alumina carrier 72 Kg with the average pore diameter of 20 nm is prepared by preparing a solution of 100L from 22.8 Kg copper nitrate trihydrate, soaking the solution into the alumina carrier, standing for 30min, drying at 110 ℃ for 10 h, and roasting at 400 ℃ for 6 h to obtain the carrier containing the accelerator Cu. Drying the carrier at 150 ℃ for 10 h, and cooling to room temperature for standby. Weighing 74.3 Kg nickel nitrate hexahydrate, 29.7 Kg nickel nitrate tetrahydrate and 2 Kg CTAB, preparing 130L solution, dipping the solution on the carrier containing the accelerator Cu, standing for 30min, and filtering out the residual solution; drying at 100deg.C for 8 h, calcining at 450deg.C for 6 h, introducing hydrogen gas at 400deg.C for 5h, and protecting the reduced catalyst with liquid.
(1) The 40wt percent 1, 4-butynediol aqueous solution which is pressurized to 2.0MPa and is at 40 ℃ enters a low pressure reactor R1, the reaction pressure is kept to be controlled at 2.0MPa, the reaction temperature is kept at 60 ℃, and the space velocity of the reaction liquid is regulated to be 4h -1 Hydrogen (99.99%) was added at a pressure of 2.0MPa and a gas space velocity of 11. 11 h -1 Carrying out first-step hydrogenation; the product is decompressed to 0.4MPa and enters a cyclone separator S1; the Raney-nickel catalyst separated from the bottom of the cyclone separator S1 is extracted from the top, and the reaction liquid is further removed by a bag filter S2; the catalyst separated from the bag filter S2 and the catalyst separated from the bottom of the cyclone S1 are circulated toThe low-pressure reactor R1 participates in the reaction again;
(2) The reaction liquid treated by the method enters a pre-separation tower T1, and the theoretical plate number is 5; at 15KPa, the operating temperature was maintained at 75deg.C. The reaction solution is cut, water, butanol and light components are distilled out from the top of the tower, and heavy components, 1, 4-butanediol, 1, 4-butylene glycol, hydroxybutanal and acetal aqueous solution are discharged from the bottom of the tower;
(3) The water, butanol and light components separated from the top of the pre-separation tower T1 enter the next separation section to extract byproduct butanol;
(4) The solution separated from the bottom of the pre-separation tower T1 is preheated by a pressurizing and high-pressure hydrogenation preheater E1 and then heated to 140 ℃, the temperature is increased to 30MPa, and the solution enters a chilled water heat-removing tubular reactor R2 from the top in a trickling mode, and the reaction temperature is controlled at 140 ℃; the reaction pressure is controlled at 30MPa and the airspeed is 0.5h -1 The method comprises the steps of carrying out a first treatment on the surface of the Further, a small amount of 1, 4-butylene glycol, hydroxybutanal and acetal are converted into 1, 4-butanediol, and the reaction product is withdrawn from the bottom R2 of the reactor. And then the 1, 4-butanediol product with the purity of 99.7 percent and the chromaticity of 2AHPA is obtained after distillation. The power electricity consumes 420 kilowatt hours per ton of 1, 4-butanediol, the steam consumes 4.5 tons per ton of 1, 4-butanediol, and the circulating cooling water consumes 320 tons per ton of 1, 4-butanediol.

Claims (6)

1. A method for preparing 1, 4-butanediol by hydrogenating 1, 4-butynediol, which is characterized by comprising the following steps:
step one, a pressurized 30-40 wt%1, 4-butynediol aqueous solution enters a low-pressure reactor, a first-step hydrogenation reaction is carried out under the action of a Raney nickel-aluminum-X catalyst, a product enters a normal-pressure cyclone separator after being depressurized, the Raney nickel-aluminum-X catalyst is separated from the bottom of the separator, a reaction liquid is extracted from the top, and catalyst particles are further removed from the reaction liquid through a bag filter; x in the Raney nickel-aluminum-X catalyst is any one of Mg, B, sr, cr, S, ti, la, sn, W, mo, fe;
step two, the reaction liquid enters a pre-separation tower; cutting the reaction liquid under vacuum, distilling water, n-butanol and light components from the top of the tower, and obtaining a mixed aqueous solution containing 1, 4-butanediol, 1, 4-butylene glycol, hydroxybutanal, acetal and heavy components from the bottom of the tower; the theoretical plate number of the pre-separation tower is 3-5, and the operating pressure is 15 KPa-25 KPa; the operation temperature is 60-75 ℃;
thirdly, water, n-butanol and light components separated from the top of the pre-separation tower enter a next separation section to extract byproduct n-butanol;
step four, the mixed aqueous solution separated from the bottom of the pre-separation tower is preheated by a pressurizing and high-pressure hydrogenation preheater and then enters a chilled water heat-removing tubular reactor, and the reaction temperature is controlled at 95-140 ℃; the reaction pressure is controlled to be 10.0-30.0 MPa, and the space velocity of the reactor liquid is 0.5-2.5 h -1 The method comprises the steps of carrying out a first treatment on the surface of the The composition of the catalyst filled in the chilled water heat removal tube reactor is as follows: the nickel content is 11-22 wt%, the accelerator content is 1-6wt%, the rest is aluminum oxide, and the accelerator is one of lanthanum, copper and magnesium elements; 1, 4-butylene glycol, hydroxybutanal and acetal are converted into 1, 4-butanediol under the action of a catalyst, reactants are extracted from the bottom of a reactor, and then the 1, 4-butanediol product is obtained after distillation.
2. The method for preparing 1, 4-butanediol by hydrogenating 1, 4-butynediol according to claim 1, wherein the method comprises the following steps: in the first step, the Raney nickel-aluminum-X catalyst used in the low-pressure reactor comprises the following components in percentage by mass (0.5-1): the addition amount of the 1, X is 1-2 wt% of the total mass of the nickel-aluminum.
3. The method for preparing 1, 4-butanediol by hydrogenating 1, 4-butynediol according to claim 1 or 2, wherein the method comprises the following steps: in the first step, the inlet solution of the low-pressure reactor is a 30-40 wt%1, 4-butynediol aqueous solution, the inlet temperature is 40-45 ℃, the inlet pressure is 1.1-4.1 MPa, and the liquid airspeed is 1-4 h -1 The method comprises the steps of carrying out a first treatment on the surface of the The inlet gas is 99.99wt% hydrogen, the inlet pressure is 1.1-4.1 MPa, and the gas space velocity is 1.5-11 h -1 The method comprises the steps of carrying out a first treatment on the surface of the The outlet pressure of the liquid is 0.4-0.8 MPa, and the outlet temperature is 60-75 ℃.
4. The process for preparing 1, 4-butanediol by hydrogenating 1, 4-butynediol according to claim 3, wherein: the low pressure reactor is a slurry bed reactor with a jacketed heat removal system.
5. The method for preparing 1, 4-butanediol by hydrogenating 1, 4-butynediol according to claim 4, wherein the method comprises the following steps: in the fourth step, the high-pressure hydrogenation preheater is a shell-and-tube heat exchanger, the liquid inlet temperature is 60-75 ℃, and the liquid outlet temperature is 95-140 ℃.
6. The method for preparing 1, 4-butanediol by hydrogenating 1, 4-butynediol according to claim 1, wherein the method comprises the following steps: the catalyst separated from the bag filter and the catalyst separated from the bottom of the cyclone were circulated to the low pressure reactor to participate in the reaction again.
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