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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赵永祥
刘绍波
李海涛
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Shanxi University
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    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/17Preparation 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
    • C07C29/172Preparation 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
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    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74Iron group metals
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts 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
    • B01J23/83Catalysts 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
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01J25/00Catalysts of the Raney type
    • B01J25/02Raney nickel
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    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/80Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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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

1,4-丁炔二醇加氢制1,4-丁二醇的方法Method for producing 1,4-butanediol by hydrogenating 1,4-butynediol

技术领域Technical field

本发明涉及1,4-丁二醇生产方法,具体属于一种1,4-丁炔二醇加氢制1,4-丁二醇的方法。The invention relates to a method for producing 1,4-butanediol, specifically a method for hydrogenating 1,4-butynediol to produce 1,4-butanediol.

背景技术Background technique

1,4- 丁二醇( 简称BDO) 是一种重要的有机和精细化工原料, 它被广泛应用于医药、化工、纺织、造纸、汽车和日用化工等领域。由1,4- 丁二醇可以生产四氢呋喃( THF)、聚对苯二甲酸丁二醇酯( PBT) 、γ-丁内脂( GBL) 和聚氨酯树脂( PU Resin) 、涂料和增塑剂等,以及作为溶剂和电镀行业的增亮剂等。1,4-Butanediol (BDO for short) is an important organic and fine chemical raw material. It is widely used in the fields of medicine, chemical industry, textile, papermaking, automobile and daily chemical industry. Tetrahydrofuran (THF), polybutylene terephthalate (PBT), γ-butyrolactone (GBL) and polyurethane resin (PU Resin), coatings and plasticizers can be produced from 1,4-butanediol. , and as a brightener in solvents and electroplating industries.

第二次世界大战前,德国已采用雷佩法以乙炔和甲醛为原料合成1,4-丁二醇。该法解决了乙炔在高压下操作的危险性,至今仍是1,4-丁二醇最主要的生产方法。60年代,日本三菱油化公司开发了由顺丁烯二酸酐催化加氢制备1,4-丁二醇的工艺,70年代该公司又开发了丁二烯乙酰氧基化法的新工艺。1971年,日本东洋曹达工业公司建立了丁二烯氯化法的生产装置。此外,美国和日本又相继研究了以丙烯或乙烯为原料的各种合成法。Before World War II, Germany had adopted the Reppe method to synthesize 1,4-butanediol using acetylene and formaldehyde as raw materials. This method solves the danger of operating acetylene under high pressure and is still the main production method of 1,4-butanediol. In the 1960s, Japan's Mitsubishi Petrochemical Company developed a process for preparing 1,4-butanediol by catalytic hydrogenation of maleic anhydride. In the 1970s, the company developed a new process for butadiene acetoxylation. In 1971, Japan's Toyo Soda Industrial Company established a production device for the butadiene chlorination method. In addition, the United States and Japan have successively studied various synthesis methods using propylene or ethylene as raw materials.

雷佩法生产过程不太复杂,成本较低。目前,此法的生产能力接近各种方法的总能力的90%,今后此法发展的关键是乙炔原料的供应和价格。The Repef method production process is less complex and less expensive. At present, the production capacity of this method is close to 90% of the total capacity of various methods. The key to the development of this method in the future is the supply and price of acetylene raw materials.

顺丁烯二酸酐加氢法,反应分两步进行,联产四氢呋喃。此法原料价高,但反应步骤少、投资低、可调节所得的联产品,因此许多国家仍在加紧进行研究开发。Maleic anhydride hydrogenation method, the reaction is carried out in two steps, and tetrahydrofuran is co-produced. This method has high raw material prices, but has fewer reaction steps, low investment, and can adjust the resulting co-products. Therefore, many countries are still stepping up research and development.

1,4-二氯丁烯法,由丁二烯生产氯丁二烯过程中,1,4-二氯丁烯是中间产物。东洋曹达工业公司开发的方法是将1,4-二氯丁烯在约110℃下用过量甲酸钠水解生成2-丁烯-1,4-二醇,转化率接近100%,选择性大于90%。水解后,游离甲酸用氢氧化钠中和。然后将2-丁烯-1,4-二醇在100℃、27MPa和镍-铝催化剂存在下加氢得 1,4-丁二醇。此法公用工程费用大,生产成本较高。1,4-Dichlorobutene method, in the process of producing chloroprene from butadiene, 1,4-dichlorobutene is an intermediate product. The method developed by Toyo Soda Industrial Co., Ltd. is to hydrolyze 1,4-dichlorobutene with excess sodium formate at about 110°C to generate 2-butene-1,4-diol. The conversion rate is close to 100% and the selectivity is greater than 90 %. After hydrolysis, the free formic acid is neutralized with sodium hydroxide. Then 2-butene-1,4-diol is hydrogenated at 100°C, 27MPa and in the presence of a nickel-aluminum catalyst to obtain 1,4-butanediol. This method has high public engineering costs and high production costs.

我国拥有丰富的煤炭资源。相较于其余生产工艺,雷佩法的原料主要为煤炭后加工供应。因此雷佩法在我国的1,4-丁二醇生产更具有实际意义。my country has abundant coal resources. Compared with other production processes, Repefa's raw materials are mainly supplied for post-processing of coal. Therefore, Repefac's 1,4-butanediol production in my country has more practical significance.

现有的雷佩法生产工艺中第一步1,4-丁炔二醇合成基本一致,只是催化剂的使用方式略有区别。而在加氢工段区别较大,第一种工艺为整个体系全部为高压固定床加氢,采用大流量30wt%~40wt%1,4-丁炔二醇水溶液循环加氢;另一种工艺为两段法,先进行低压加氢后加成产物再进行高压加氢彻底转化;两种方法相比,第二种在保证转化率和产品质量的情况下节约了加氢工段能量消耗;The first step of 1,4-butynediol synthesis in the existing Rappe production process is basically the same, but the use of the catalyst is slightly different. There is a big difference in the hydrogenation section. The first process is that the entire system is high-pressure fixed bed hydrogenation, using a large flow rate of 30wt%~40wt% 1,4-butynediol aqueous solution for cyclic hydrogenation; the other process is The two-stage method first performs low-pressure hydrogenation, then adds the product, and then performs high-pressure hydrogenation for complete conversion. Compared with the two methods, the second method saves energy consumption in the hydrogenation section while ensuring the conversion rate and product quality;

传统的两步法加氢制1,4-丁二醇的过程如下:第一步(也称为一段加氢)一般采用悬浮床(或鼓泡淤浆床),使用雷尼-镍催化剂,在50~80℃,1~3MPa氢气压力下进行低压加氢,将浓度30wt%~40wt%1,4-丁炔二醇水溶液加氢为1,4-丁二醇水溶液,同时溶液中含有正丁醇,不饱和加氢产物1,4-丁烯二醇,1,4-丁烯二醇异构化产物4-羟基丁醛及醛与醇经缩合反应得到的缩醛及其他高沸物和低沸物;由于4-羟基丁醛及缩醛及1,4-丁烯二醇无法通过精馏的方法脱除,存在产品中影响产品纯度与质量,需要进行进一步的高压加氢脱除;第二步(二段加氢)将一段的产物溶液采用固定床反应器,以负载镍为催化剂,在反应温度110~160℃,氢气压力12~21MPa下进行加氢,主要涉及物料中少量的1,4-丁烯二醇、异构化产物羟基丁醛及缩醛的进一步加氢转化,以提高1,4-丁二醇的产率和减少杂质的存在。The traditional two-step hydrogenation process to produce 1,4-butanediol is as follows: the first step (also called one-stage hydrogenation) generally adopts a suspended bed (or bubbling slurry bed) and uses a Raney-nickel catalyst. Perform low-pressure hydrogenation at 50~80℃ and 1~3MPa hydrogen pressure to hydrogenate 1,4-butynediol aqueous solution with a concentration of 30wt%~40wt% into 1,4-butanediol aqueous solution, and the solution contains normal Butanol, 1,4-butenediol, the unsaturated hydrogenation product, 4-hydroxybutyraldehyde, the isomerization product of 1,4-butenediol, acetals obtained by the condensation reaction of aldehydes and alcohols, and other high boilers and low boiling substances; since 4-hydroxybutyraldehyde, acetal and 1,4-butenediol cannot be removed by distillation, their presence in the product affects the purity and quality of the product and requires further high-pressure hydrogenation removal. ; The second step (two-stage hydrogenation) uses a fixed-bed reactor with supported nickel as the catalyst to hydrogenate the product solution of the first stage at a reaction temperature of 110 to 160°C and a hydrogen pressure of 12 to 21MPa, mainly involving a small amount of the material. Further hydrogenation and conversion of 1,4-butenediol, isomerization product hydroxybutyraldehyde and acetal to increase the yield of 1,4-butanediol and reduce the presence of impurities.

以上过程在现有技术中已被多次公开,但是以上工艺在第二段加氢的过程中因为传统固定床滴流反应体系的撤热要求,仍然采用低浓度、大流量的加氢过程,体系中存在大量的水(60wt%~70wt%),因而增加了体系的能耗。The above process has been disclosed many times in the prior art. However, in the second stage of hydrogenation, due to the heat removal requirements of the traditional fixed bed trickle reaction system, a low concentration and large flow hydrogenation process is still used. There is a large amount of water (60wt%~70wt%) in the system, which increases the energy consumption of the system.

发明内容Contents of the invention

本发明要解决的技术问题是提供一种1,4-丁炔二醇加氢制1,4-丁二醇的方法,通过提前分离以达到降低能耗的目的。The technical problem to be solved by the present invention is to provide a method for hydrogenating 1,4-butynediol to produce 1,4-butanediol, which can achieve the purpose of reducing energy consumption through early separation.

为解决以上技术问题,本发明采用的技术方案是:一种1,4-丁炔二醇加氢制1,4-丁二醇的方法,包括:In order to solve the above technical problems, the technical solution adopted by the present invention is: a method for hydrogenating 1,4-butynediol to produce 1,4-butanediol, which includes:

步骤一,经过加压的30wt%~40wt%的1,4-丁炔二醇水溶液进入低压反应器,在雷尼镍-铝-X催化剂作用下,进行第一步加氢反应,产物经过减压后进入常压的旋风分离器,分离器底部分离出雷尼镍-铝-X催化剂,顶部采出反应液,反应液通过袋式过滤器进一步去除催化剂颗粒;Step 1: Pressurized 30wt% to 40wt% 1,4-butynediol aqueous solution enters the low-pressure reactor, and under the action of Raney Nickel-Aluminum-X catalyst, the first step of hydrogenation reaction is carried out, and the product is reduced After being pressed, it enters a cyclone separator at normal pressure. The Raney Nickel-Aluminum-X catalyst is separated at the bottom of the separator, and the reaction liquid is taken out from the top. The reaction liquid passes through a bag filter to further remove catalyst particles;

步骤二,反应液进入预分离塔;在真空状态下反应液被切分,水、正丁醇、轻组分从塔顶馏出,从塔底出来含有1,4-丁二醇、1,4-丁烯二醇、羟基丁醛、缩醛和重组分的混合水溶液;In step two, the reaction liquid enters the pre-separation tower; the reaction liquid is cut under vacuum, water, n-butanol, and light components are distilled from the top of the tower, and the bottom of the tower contains 1,4-butanediol, 1, Mixed aqueous solution of 4-butenediol, hydroxybutyraldehyde, acetal and heavy components;

步骤三,从预分离塔顶部分离出的水、正丁醇、轻组分进入下一分离工段提取副产品正丁醇;Step 3: The water, n-butanol and light components separated from the top of the pre-separation tower enter the next separation section to extract the by-product n-butanol;

步骤四,从预分离塔底部分离出的混合水溶液通过加压和高压加氢预热器预热后进入冷冻水撤热列管式反应器中,将1,4-丁烯二醇、羟基丁醛及缩醛在催化剂作用下转化为1,4-丁二醇,反应物从反应器底部采出,再经过蒸馏后得1,4-丁二醇产品。Step 4: The mixed aqueous solution separated from the bottom of the pre-separation tower is preheated by pressurization and high-pressure hydrogenation preheater and then enters the chilled water heat removal tube reactor, and 1,4-butenediol and hydroxybutane are Aldehydes and acetals are converted into 1,4-butanediol under the action of catalysts. The reactants are taken out from the bottom of the reactor and then distilled to obtain the 1,4-butanediol product.

进一步地,步骤一中,低压反应器中所用的雷尼镍-铝-X催化剂由组成为镍铝质量比为(0.5-1):1、X 的添加量为镍铝总质量的1wt%-2wt %的金属粉末经25%的NaOH处理后得到;其中 X 为Mg、B、Sr、Cr、S、Ti、La、Sn、W、Mo、Fe 中的任意一种。优选地,X为Mg。Further, in step one, the Raney nickel-aluminum-X catalyst used in the low-pressure reactor is composed of a nickel-aluminum mass ratio of (0.5-1): 1. The amount of X added is 1wt%- of the total mass of nickel-aluminum. 2wt% metal powder is obtained after being treated with 25% NaOH; where X is any one of Mg, B, Sr, Cr, S, Ti, La, Sn, W, Mo, and Fe. Preferably, X is Mg.

进一步地,步骤一中,低压反应器进口溶液为30wt%~40wt%的1,4-丁炔二醇水溶液,入口温度为40℃~45℃,入口压力为1.1~4.1MPa,液体空速为1~4h-1;入口气体为99.99wt%的氢气,入口压力为1.1~4.1MPa,气体空速为11~1.5 h-1;液体出口压力为0.4~0.8MPa,出口温度为60℃~75℃。Further, in step one, the inlet solution of the low-pressure reactor is a 30wt%~40wt% 1,4-butynediol aqueous solution, the inlet temperature is 40°C~45°C, the inlet pressure is 1.1~4.1MPa, and the liquid space velocity is 1~4h -1 ; the inlet gas is 99.99wt% hydrogen, the inlet pressure is 1.1~4.1MPa, the gas space velocity is 11~1.5 h -1 ; the liquid outlet pressure is 0.4~0.8MPa, the outlet temperature is 60℃~75 ℃.

进一步地,低压反应器为带有夹套撤热系统的淤浆床反应器。Further, the low-pressure reactor is a slurry bed reactor with a jacketed heat removal system.

进一步地,步骤二中,所述的预分离塔,其理论板数为3~5,操作压力为15KPa~25KPa;操作温度为60℃~75℃。Further, in step two, the number of theoretical plates of the pre-separation tower is 3 to 5, the operating pressure is 15KPa to 25KPa, and the operating temperature is 60°C to 75°C.

进一步地,步骤四中,所述的高压加氢预热器为管壳式换热器,液体入口温度为60℃~75℃,出口温度为95℃~140℃。Further, in step four, the high-pressure hydrogenation preheater is a shell-and-tube heat exchanger, the liquid inlet temperature is 60°C to 75°C, and the outlet temperature is 95°C to 140°C.

进一步地,步骤四中,冷冻水撤热列管式反应器所装填催化剂的组成为:镍含量11-22 wt%,促进剂含量1~6 wt%,其余为氧化铝,所述的促进剂是镧、铜、镁元素中的一种。Further, in step four, the composition of the catalyst filled in the chilled water heat removal tube reactor is: nickel content 11-22 wt%, accelerator content 1-6 wt%, the rest is alumina, and the accelerator It is one of the elements lanthanum, copper, and magnesium.

进一步地,冷冻水撤热列管式反应器R为列管式反应器,催化剂装填在列管内,壳程由冷冻水撤热,反应温度控制在95℃~140℃;反应压力控制在10.0~30.0MPa; 反应器液体空速0.5~2.5h-1Further, the chilled water heat removal tube reactor R is a tube reactor, the catalyst is loaded in the tubes, the shell side is heat removed by the chilled water, the reaction temperature is controlled at 95°C ~ 140°C; the reaction pressure is controlled at 10.0 ~ 30.0MPa; reactor liquid space velocity 0.5~2.5h -1 .

进一步地,从袋式过滤器分离出的催化剂和旋风分离器底部分离出的催化剂循环至低压反应器再次参加反应。Further, the catalyst separated from the bag filter and the catalyst separated from the bottom of the cyclone separator are circulated to the low-pressure reactor to participate in the reaction again.

本发明中,本发明人通过催化剂比选试验、活性评价、理论计算和软件模拟,掌握了低压1,4-丁炔二醇加氢和高压把关加氢反应的反应规律,筛选出了适合于中压1,4-丁炔二醇加氢合适的催化剂和高浓度下高压把关加氢催化剂的合理反应形式,将现有两段式1,4-丁炔二醇加氢过程中存在的高能耗问题,通过提前分离和改变加氢反应器形式,达到即完成工艺目标,又降低能耗的目的。In the present invention, the inventor mastered the reaction rules of low-pressure 1,4-butynediol hydrogenation and high-pressure check hydrogenation through catalyst comparison and selection tests, activity evaluation, theoretical calculations and software simulations, and screened out suitable Suitable catalysts for medium-pressure 1,4-butynediol hydrogenation and reasonable reaction forms of high-pressure check hydrogenation catalysts at high concentrations can eliminate the high-energy problems existing in the existing two-stage 1,4-butynediol hydrogenation process. To solve the problem of energy consumption, by separating in advance and changing the form of the hydrogenation reactor, we can achieve the goal of completing the process goals and reducing energy consumption.

具体而言,本发明与现有技术相比具有如下优点:Specifically, the present invention has the following advantages compared with the prior art:

(1) 现有技术低压反应器物料出口温度为60℃~75℃,高压加氢前需将含有60%左右的水、丁醇等组分的物料加热到95℃~140℃,耗费大量的能量。本发明无需加热条件下,提前分离低压加氢过后的溶液,在高压加氢前去除了60wt%左右的反应液重量,进而大大的降低了高压加氢工段的能量消耗。同时,高压加氢段的物料处理量相应下降,相同的1,4-丁二醇处理量时,整个高压加压设备的尺寸减小,投资大幅下降。(1) The material outlet temperature of the existing low-pressure reactor is 60°C to 75°C. Before high-pressure hydrogenation, the material containing about 60% water, butanol and other components needs to be heated to 95°C to 140°C, which consumes a lot of energy. energy. The present invention separates the solution after low-pressure hydrogenation in advance without heating, and removes about 60wt% of the weight of the reaction solution before high-pressure hydrogenation, thus greatly reducing the energy consumption of the high-pressure hydrogenation section. At the same time, the material processing capacity of the high-pressure hydrogenation section decreases accordingly. For the same 1,4-butanediol processing capacity, the size of the entire high-pressure pressurizing equipment is reduced, and the investment is significantly reduced.

(2)高压物料的浓缩,反应物浓度增加不仅需要更高的催化剂活性,也使得反应放热加剧,对反应器撤热提出更高的要求。现有技术高压反应采用普通的Ni/Al2O3催化剂,催化剂活性低,不能满足高浓度反应物料的活性需求。采用的固定床塔式反应器,撤热效率低,很容易造成催化剂床层飞温,导致催化剂不可逆失活。本发明一方面,采用了最新研发的新型高效加氢催化剂,该催化剂镍含量11-22 wt%,促进剂含量1~6 wt%,其余为氧化铝,所述的促进剂是镧、铜、镁元素中的一种。催化剂活性组分镍通过混合盐溶液浸渍的方式被引入到载体中,混合镍盐由无机镍盐与有机镍盐混合而成,由于阴离子间的协同与竞争吸附作用可以促使活性组分均匀沉积到催化剂载体的内表面,得到高分散的催化剂产品。同时,在浸渍液中加入适量的表面活性剂聚乙二醇或CTAB,一方面起到增加溶解度的作用,另一方面进一步促进了镍物种的分散,焙烧过程产生的积碳还可以阻止活性组分团聚,同时调节活性组分与载体间的相互作用。由于采用特殊的催化剂制备方法,所得催化剂在较高的活性组分负载量下保持了高的分散度,该催化剂具有适宜的表面酸碱性、合适的孔结构、合适的金属与载体的相互作用。因而在高的加氢中表现出高的催化活性与选择性,并具有长的催化剂使用寿命。(2) The concentration of high-pressure materials and the increase in reactant concentration not only require higher catalyst activity, but also intensify the heat release of the reaction, placing higher requirements on reactor heat removal. The existing high-pressure reaction uses ordinary Ni/Al 2 O 3 catalyst, which has low catalyst activity and cannot meet the activity requirements of high-concentration reaction materials. The fixed-bed tower reactor used has low heat removal efficiency, which can easily cause the catalyst bed to overheat, leading to irreversible deactivation of the catalyst. On the one hand, the present invention uses a newly developed new high-efficiency hydrogenation catalyst. The nickel content of the catalyst is 11-22 wt%, the accelerator content is 1-6 wt%, and the rest is alumina. The accelerator is lanthanum, copper, One of the elements magnesium. The active component of the catalyst, nickel, is introduced into the carrier by impregnation with a mixed salt solution. The mixed nickel salt is composed of a mixture of inorganic nickel salt and organic nickel salt. Due to the synergistic and competitive adsorption between anions, the active component can be uniformly deposited into the carrier. The inner surface of the catalyst carrier obtains a highly dispersed catalyst product. At the same time, adding an appropriate amount of surfactant polyethylene glycol or CTAB to the impregnation solution can increase the solubility on the one hand, and further promote the dispersion of nickel species on the other hand. The carbon deposits generated during the roasting process can also prevent the active group from forming. It can separate agglomeration and regulate the interaction between active components and carrier. Due to the special catalyst preparation method, the resulting catalyst maintains a high degree of dispersion under a high loading of active components. The catalyst has suitable surface acidity and alkalinity, suitable pore structure, and suitable interaction between metal and carrier. . Therefore, it shows high catalytic activity and selectivity in high hydrogenation, and has a long catalyst service life.

(3)针对高浓度物料放热加剧的问题,通过对传统高压加氢反应器类型进行优选,将原来简单的固定床塔式反应器改为撤热效果更好的高压列管式反应器,使在高浓度反应的过程中顺利撤出反应热。(3) In order to solve the problem of increased heat release of high-concentration materials, by optimizing the type of traditional high-pressure hydrogenation reactor, the original simple fixed-bed tower reactor was changed to a high-pressure tubular reactor with better heat removal effect. This enables the reaction heat to be smoothly withdrawn during high-concentration reactions.

本发明通过上述工艺流程之后可得产品纯度≥99.5%,色度≤10AHPA的1,4-丁二醇产品。对公用工程消耗大幅下降,动力电消耗低于420 千瓦时/吨1,4-丁二醇,蒸汽消耗低于4.5 吨/吨1,4-丁二醇,循环冷却水消耗低于320 吨/吨1,4-丁二醇。After passing through the above process flow, the present invention can obtain a 1,4-butanediol product with a product purity of ≥99.5% and a color of ≤10AHPA. Consumption of public works has been significantly reduced. Power consumption is less than 420 kWh/ton of 1,4-butanediol, steam consumption is less than 4.5 tons/ton of 1,4-butanediol, and circulating cooling water consumption is less than 320 tons/ton. tons of 1,4-butanediol.

附图说明Description of drawings

图1为现有技术中1,4-丁炔二醇加氢制1,4-丁二醇的流程图。Figure 1 is a flow chart of hydrogenation of 1,4-butynediol to 1,4-butanediol in the prior art.

图2为本发明所述的1,4-丁炔二醇加氢制1,4-丁二醇的流程图。Figure 2 is a flow chart of the hydrogenation of 1,4-butynediol to 1,4-butanediol according to the present invention.

具体实施方式Detailed ways

下面通过一些实施例对本发明要求保护的技术方案作进一步说明。但是,实施例和对比例是用于解释本发明实施方案,并不超出本发明主题的范围,本发明保护范围不受所述实施例的限定。The technical solution claimed by the present invention will be further described below through some examples. However, the examples and comparative examples are used to explain the embodiments of the present invention and do not exceed the scope of the subject matter of the present invention. The protection scope of the present invention is not limited by the examples.

以下实施例中,雷尼镍-铝-X催化剂的制备方法可参考公开号CN 102744083 A的专利文献。冷冻水撤热列管式反应器所装填催化剂的制备方法可参考公开号CN101306368A的专利文献。In the following examples, the preparation method of the Raney nickel-aluminum-X catalyst can be referred to the patent document with publication number CN 102744083 A. For the preparation method of the catalyst packed in the chilled water heat removal tubular reactor, please refer to the patent document with publication number CN101306368A.

除非另作特殊说明,本发明中所用材料、试剂均可从本领域商业化产品中获得。Unless otherwise specified, the materials and reagents used in the present invention can be obtained from commercial products in the field.

实施例1Example 1

本实施例中,低压反应器R1所用的雷尼镍-铝-X催化剂组成:镍铝质量比为0.5:1,X 的添加量为镍铝总质量的1wt%,其中所述的X为Mg。制备过程如下:分别称取 250kg 的Ni 块,500kg 的 Al 块以及 7.5kg 的Mg置于中大型熔炉中,打开电流,待 Ni、Al及Mg熔化之后,在 900℃保温熔炼 60min 之后,倒入水中冷却 ;冷却后得到的催化剂碾磨至 200目的粉末 ;分批次称取适量的催化剂粉末分批次加入质量浓度为 25% 的NaOH 溶液中混合均匀,随后控制温度在 60℃反应 30min,反应完毕之后,用蒸馏水洗涤 3次、再用无水乙醇洗涤至中性。In this embodiment, the composition of the Raney nickel-aluminum-X catalyst used in the low-pressure reactor R1: the nickel-aluminum mass ratio is 0.5:1, and the amount of X added is 1wt% of the total mass of nickel-aluminum, where the X is Mg . The preparation process is as follows: Weigh 250kg of Ni block, 500kg of Al block and 7.5kg of Mg respectively in a medium and large furnace, turn on the current, wait until Ni, Al and Mg are melted, keep melting at 900℃ for 60min, then pour Cool in water; grind the catalyst obtained after cooling to a powder of 200 mesh; weigh an appropriate amount of catalyst powder in batches and add it to a NaOH solution with a mass concentration of 25% in batches, mix evenly, and then control the temperature at 60°C for 30 minutes to react. After completion, wash with distilled water three times and then with absolute ethanol until neutral.

冷冻水撤热列管式反应器R2所装填的催化剂组成:镍含量11 wt%,促进剂Mg含量1wt%,其余为氧化铝。该催化剂按下述骤制备。取比表面为220 m2·g-1,孔容为0.7 cm3·g-1,平均孔径为12 nm的氧化铝载体88 Kg,取10.6 Kg六水合硝酸镁,配制成100 L溶液,将溶液浸渍到氧化铝载体中,静置30 min,后经120℃干燥12 h,500 ℃焙烧6 h后,得到含促进剂Mg的载体。将上述载体经150℃抽真空处理10 min,后降至室温备用。称取29.7 Kg六水合硝酸镍、21.3 Kg四水合硝酸镍以及2 Kg聚乙二醇,配制成100 L溶液,浸渍到上述含促进剂Mg的载体上,静置20 min,滤去剩余溶液;经80 ℃干燥10 h后,250 ℃焙烧10 h,然后通入氢气450 ℃还原5 h,还原后的催化剂经氧气钝化,备用。The composition of the catalyst packed in the chilled water heat removal tube reactor R2 is: nickel content 11 wt%, accelerator Mg content 1wt%, and the rest is alumina. The catalyst was prepared as follows. Take 88 Kg of alumina carrier with a specific surface of 220 m 2 ·g -1 , a pore volume of 0.7 cm 3 ·g -1 and an average pore diameter of 12 nm. Take 10.6 Kg of magnesium nitrate hexahydrate and prepare a 100 L solution. The solution was immersed in the alumina carrier, left to stand for 30 minutes, dried at 120°C for 12 hours, and calcined at 500°C for 6 hours to obtain a carrier containing the accelerator Mg. The above carrier was vacuumed at 150°C for 10 min, and then lowered to room temperature for later use. Weigh 29.7 Kg of nickel nitrate hexahydrate, 21.3 Kg of nickel nitrate tetrahydrate and 2 Kg of polyethylene glycol, prepare a 100 L solution, dip it into the above carrier containing the accelerator Mg, let it stand for 20 minutes, and filter out the remaining solution; After drying at 80°C for 10 hours, it was calcined at 250°C for 10 hours, and then reduced by introducing hydrogen at 450°C for 5 hours. The reduced catalyst was passivated by oxygen and is ready for use.

(1)经过加压至4.1MPa,40℃的30wt%的1,4丁炔二醇水溶液进入低压反应器R1,保持反应压力控制在4.1MPa,并保持反应温度为60℃,调节反应液体空速为1h-1,加入氢气(99.99%)的压力为4.1 MPa,气体空速1.5 h-1,进行第一步加氢;产物经过减压至0.4 MPa进入旋风分离器S1;旋风分离器S1底部分离出的雷尼镍-铝-X催化剂,顶部采出反应液,该反应液通过袋式过滤器S2进一步去除催化剂颗粒;从袋式过滤器S2分离出的催化剂和旋风分离器S1底部分离出的催化剂循环至低压反应器R1再次参加反应;(1) After being pressurized to 4.1MPa, a 30wt% 1,4-butynediol aqueous solution at 40°C enters the low-pressure reactor R1. Keep the reaction pressure at 4.1MPa and the reaction temperature at 60°C. Adjust the reaction liquid air. The speed is 1h -1 , the pressure of adding hydrogen (99.99%) is 4.1 MPa, the gas space velocity is 1.5 h -1 , and the first step of hydrogenation is carried out; the product is decompressed to 0.4 MPa and enters the cyclone separator S1; cyclone separator S1 The Raney Nickel-Aluminum-X catalyst is separated from the bottom, and the reaction liquid is taken out from the top. The reaction liquid is further removed from the catalyst particles through the bag filter S2; the catalyst separated from the bag filter S2 is separated from the bottom of the cyclone separator S1 The outgoing catalyst is circulated to the low-pressure reactor R1 to participate in the reaction again;

(2)通过上述处理的反应液进入预分离塔T1,理论板数为5块,在15KPa,操作温度保持在75℃。反应液被切分,水、丁醇、轻组分从塔顶馏出,1,4-丁二醇、1,4-丁烯二醇、羟基丁醛及缩醛和重组分的混合水溶液从塔底出来;(2) The reaction liquid after the above treatment enters the pre-separation tower T1, with 5 theoretical plates, at 15KPa, and the operating temperature is maintained at 75°C. The reaction liquid is cut, water, butanol, and light components are distilled from the top of the tower, and the mixed aqueous solution of 1,4-butanediol, 1,4-butenediol, hydroxybutyraldehyde, acetal and heavy components is distilled from the top of the tower. Come out from the bottom of the tower;

(3)从预分离塔T1顶部分离出的水、丁醇、轻组分进入下一分离工段提取副产品丁醇;(3) The water, butanol and light components separated from the top of the pre-separation tower T1 enter the next separation section to extract the by-product butanol;

(4)从预分离塔T1底部分离出的混合水溶液通过加压和高压加氢预热器E1预热后加热至120℃、升压至20 MPa,从顶部以滴流方式进入冷冻水撤热列管式反应器R2中,反应温度控制在140℃;反应压力控制在20MPa;空速0.5h-1;进一步将少量的1,4-丁烯二醇、羟基丁醛及缩醛转化为1,4丁二醇,反应物从反应器R2底部采出。再经过蒸馏后得产品纯度为99.6%,色度等于5AHPA的1,4-丁二醇产品。动力电消耗400 千瓦时/吨1,4-丁二醇,蒸汽消耗 4.1 吨/吨1,4-丁二醇,循环冷却水消耗 300 吨/吨1,4-丁二醇。(4) The mixed aqueous solution separated from the bottom of the pre-separation tower T1 is preheated by the pressurized and high-pressure hydrogenation preheater E1, then heated to 120°C, the pressure raised to 20 MPa, and then enters the chilled water in a trickle manner from the top to remove heat. In the tubular reactor R2, the reaction temperature is controlled at 140°C; the reaction pressure is controlled at 20MPa; the space velocity is 0.5h -1 ; a small amount of 1,4-butenediol, hydroxybutyraldehyde and acetal are further converted into 1 ,4 butanediol, the reactant is taken out from the bottom of reactor R2. After further distillation, a 1,4-butanediol product with a purity of 99.6% and a color equal to 5AHPA is obtained. Power electricity consumption is 400 kWh/ton of 1,4-butanediol, steam consumption is 4.1 tons/ton of 1,4-butanediol, and circulating cooling water consumption is 300 tons/ton of 1,4-butanediol.

对比实施例1Comparative Example 1

本实施例中,采用与实施例1相同的雷尼镍-铝-X催化剂用于低压反应器,以及 镍含量11 wt%,促进剂Mg含量1 wt%,其余为氧化铝的高压加氢催化剂。采用现有的加氢工艺:In this example, the same Raney nickel-aluminum-X catalyst as in Example 1 is used in the low-pressure reactor, and the nickel content is 11 wt%, the accelerator Mg content is 1 wt%, and the rest is a high-pressure hydrogenation catalyst of alumina. . Using existing hydrogenation processes:

(1)经过加压至4.1MPa,40℃的30wt%的1,4丁炔二醇水溶液进入低压加氢反应器,保持反应压力控制在4.1MPa,并保持反应温度为60℃,调节反应液体空速为1h-1,加入氢气(99.99%)的压力为4.1 MPa,气体空速1.5 h-1,进行第一步加氢;产物经过减压至0.4 MPa进入分离器,分离出的催化剂循环至低压反应器再次参加反应;(1) After pressurizing to 4.1MPa, a 30wt% 1,4-butynediol aqueous solution at 40°C enters the low-pressure hydrogenation reactor. Keep the reaction pressure at 4.1MPa and the reaction temperature at 60°C. Adjust the reaction liquid The space velocity is 1h -1 , the pressure of adding hydrogen (99.99%) is 4.1 MPa, the gas space velocity is 1.5 h -1 , and the first step of hydrogenation is carried out; the product is decompressed to 0.4 MPa and enters the separator, and the separated catalyst is recycled to the low-pressure reactor to participate in the reaction again;

(2)分离出的物料通过加压和高压加氢预热器预热后加热至120℃、升压至20MPa,从顶部以滴流方式进入固定床反应器中,反应温度控制在140℃;反应压力控制在20MPa;空速0.5h-1;进一步将少量的1,4-丁烯二醇、羟基丁醛及缩醛转化为1,4丁二醇,反应物从反应器底部采出。再经过蒸馏后得产品纯度为99.5%,色度等于5 AHPA的1,4-丁二醇产品。动力电消耗485 千瓦时/吨1,4-丁二醇,蒸汽消耗 5.3 吨/吨1,4-丁二醇,循环冷却水消耗 353 吨/吨1,4-丁二醇。(2) The separated material is preheated by pressurization and high-pressure hydrogenation preheater, then heated to 120°C, the pressure is raised to 20MPa, and then enters the fixed-bed reactor in a trickle manner from the top, and the reaction temperature is controlled at 140°C; The reaction pressure is controlled at 20MPa; the space velocity is 0.5h -1 ; a small amount of 1,4-butenediol, hydroxybutyraldehyde and acetal are further converted into 1,4-butanediol, and the reactants are taken out from the bottom of the reactor. After further distillation, a 1,4-butanediol product with a purity of 99.5% and a color equal to 5 AHPA is obtained. The power consumption is 485 kWh/ton of 1,4-butanediol, the steam consumption is 5.3 tons/ton of 1,4-butanediol, and the circulating cooling water consumption is 353 tons/ton of 1,4-butanediol.

实施例2Example 2

本实施例中,低压反应器R1所用的雷尼镍-铝-X催化剂组成:镍铝质量比为0.6:1,X 的添加量为镍铝总质量的1wt%,其中所述的X为Mg。制备过程如下:分别称取 300kg 的Ni 块,500kg 的 Al 块以及 8kg 的Mg置于中大型熔炉中,打开电流,待 Ni、Al及Mg熔化之后,在 900℃保温熔炼 60min 之后,倒入水中冷却;冷却后得到的催化剂碾磨至 200 目的粉末 ;分批次称取适量的催化剂粉末分批次加入质量浓度为25% 的NaOH 溶液中混合均匀,随后控制温度在 60℃反应 30min,反应完毕之后,用蒸馏水洗涤 3次、再用无水乙醇洗涤至中性。In this example, the composition of the Raney nickel-aluminum-X catalyst used in the low-pressure reactor R1: the nickel-aluminum mass ratio is 0.6:1, and the amount of X added is 1wt% of the total mass of nickel-aluminum, where the X is Mg . The preparation process is as follows: Weigh 300kg of Ni block, 500kg of Al block and 8kg of Mg respectively in a medium and large furnace, turn on the current, wait for Ni, Al and Mg to melt, then keep smelting at 900°C for 60 minutes, then pour into water Cool; grind the catalyst obtained after cooling to a powder of 200 mesh; weigh an appropriate amount of catalyst powder in batches, add it to a NaOH solution with a mass concentration of 25% in batches, mix evenly, and then control the temperature at 60°C for 30 minutes to complete the reaction. After that, it was washed three times with distilled water and then washed with absolute ethanol until it was neutral.

冷冻水撤热列管式反应器R2所装填的催化剂组成:镍含量13 wt%,促进剂La含量3wt%,其余为氧化铝。该催化剂按下述步骤制备:取比表面为300 m2·g-1,孔容为1.1 cm3·g-1,平均孔径为17 nm的氧化铝载体84 Kg,取9.4 Kg六水合硝酸镧,配制成120 L溶液,将溶液浸渍到氧化铝载体中,静置20 min,后经110℃干燥10 h,400 ℃焙烧6 h后,得到含促进剂La的载体。将上述载体经150℃干燥10 h,后降至室温备用。称取39.6 Kg六水合硝酸镍、17.0 Kg四水合硝酸镍以及3Kg CTAB,配制成120 L溶液,浸渍到上述含促进剂La的载体上,静置30 min,滤去剩余溶液;经100 ℃干燥8 h后,450 ℃焙烧6 h,然后通入氢气400 ℃还原5 h,还原后的催化剂经液体保护,备用。The composition of the catalyst filled in the chilled water heat removal tube reactor R2 is: nickel content 13 wt%, accelerator La content 3wt%, and the rest is alumina. The catalyst is prepared according to the following steps: take 84 Kg of an alumina carrier with a specific surface of 300 m 2 ·g -1 , a pore volume of 1.1 cm 3 ·g -1 and an average pore diameter of 17 nm, and 9.4 Kg of lanthanum nitrate hexahydrate. , prepare a 120 L solution, immerse the solution into the alumina carrier, let it stand for 20 minutes, then dry at 110°C for 10 h, and roast at 400°C for 6 h to obtain a carrier containing accelerator La. The above carrier was dried at 150°C for 10 h, and then lowered to room temperature for use. Weigh 39.6 Kg of nickel nitrate hexahydrate, 17.0 Kg of nickel nitrate tetrahydrate and 3Kg of CTAB, prepare a 120 L solution, dip it into the above carrier containing accelerator La, let it stand for 30 minutes, filter out the remaining solution, and dry at 100°C After 8 hours, it was calcined at 450°C for 6 hours, and then hydrogen was introduced at 400°C for reduction for 5 hours. The reduced catalyst was protected by liquid and is ready for use.

(1)经过加压至3.0MPa,40℃的35wt%的1,4丁炔二醇水溶液进入低压反应器R1,保持反应压力控制在3.0MPa,并保持反应温度为60℃,调节反应液体空速为2h-1,加入氢气(99.99%)的压力为3 MPa,气体空速3 h-1,进行第一步加氢;产物经过减压后至0.4MPa进入旋风分离器S1;旋风分离器S1底部分离出雷尼镍-铝-X催化剂,顶部采出反应液,该反应液通过袋式过滤器S2进一步去除催化剂颗粒;从袋式过滤器S2分离出的催化剂和旋风分离器S1底部分离出的催化剂循环至低压反应器R1再次参加反应;(1) After being pressurized to 3.0MPa, a 35wt% 1,4-butynediol aqueous solution at 40°C enters the low-pressure reactor R1. Keep the reaction pressure at 3.0MPa and the reaction temperature at 60°C. Adjust the reaction liquid air. The speed is 2h -1 , the pressure of adding hydrogen (99.99%) is 3 MPa, the gas space velocity is 3 h -1 , and the first step of hydrogenation is carried out; the product enters the cyclone separator S1 after decompression to 0.4MPa; cyclone separator The Raney Nickel-Aluminum-X catalyst is separated from the bottom of S1, and the reaction liquid is taken out from the top. The reaction liquid is further removed by the bag filter S2; the catalyst separated from the bag filter S2 is separated from the bottom of the cyclone separator S1. The outgoing catalyst is circulated to the low-pressure reactor R1 to participate in the reaction again;

(2)通过上述处理的反应液进入预分离塔T1,理论板数为4;在20KPa,操作温度保持在70℃。反应液被切分,水、丁醇、轻组分从塔顶馏出,重组分、1,4-丁二醇、1,4-丁烯二醇、羟基丁醛及缩醛的水溶液从塔底出来;(2) The reaction liquid after the above treatment enters the pre-separation tower T1, with a theoretical plate number of 4; at 20KPa, the operating temperature is maintained at 70°C. The reaction liquid is divided, water, butanol, and light components are distilled from the top of the tower, and the heavy components, 1,4-butanediol, 1,4-butenediol, hydroxybutyraldehyde and acetal aqueous solutions are distilled from the top of the tower. bottom out;

(3)从预分离塔T1顶部分离出的水、丁醇、轻组分进入下一分离工段提取副产品丁醇;(3) The water, butanol and light components separated from the top of the pre-separation tower T1 enter the next separation section to extract the by-product butanol;

(4)从预分离塔T1底部分离出的溶液通过加压和高压加氢预热器E1预热后加热至120℃、升压至25MPa,从顶部以滴流方式进入冷冻水撤热列管式反应器R2中,反应温度控制在130℃;反应压力控制在25MPa;空速1.0h-1;进一步将少量的1,4-丁烯二醇、羟基丁醛及缩醛转化为1,4丁二醇,反应物从反应器R2底部采出。再经过蒸馏后得产品纯度为99.7%,色度等于3AHPA的1,4-丁二醇产品。动力电消耗400 千瓦时/吨1,4-丁二醇,蒸汽消耗 4.1 吨/吨1,4-丁二醇,循环冷却水消耗 300 吨/吨1,4-丁二醇。(4) The solution separated from the bottom of the pre-separation tower T1 is preheated by the pressurized and high-pressure hydrogenation preheater E1, heated to 120°C, raised to 25MPa, and enters the chilled water heat removal tube from the top in a trickle manner. In the type reactor R2, the reaction temperature is controlled at 130°C; the reaction pressure is controlled at 25MPa; the space velocity is 1.0h -1 ; a small amount of 1,4-butenediol, hydroxybutyraldehyde and acetal are further converted into 1,4 Butanediol, the reactant is taken out from the bottom of reactor R2. After further distillation, a 1,4-butanediol product with a purity of 99.7% and a color equal to 3AHPA is obtained. Power electricity consumption is 400 kWh/ton of 1,4-butanediol, steam consumption is 4.1 tons/ton of 1,4-butanediol, and circulating cooling water consumption is 300 tons/ton of 1,4-butanediol.

实施例3Example 3

本实施例中,低压反应器R1所用的雷尼镍-铝-X催化剂组成:镍铝质量比为0.7:1,X 的添加量为镍铝总质量的1wt%,其中所述的X为Mg。制作过程如下:分别称取 350kg 的Ni 块,500kg 的 Al 块以及 8.5kg 的Mg置于中大型熔炉中,打开电流,待 Ni、Al及Mg熔化之后,在 900℃保温熔炼 60min 之后,倒入水中冷却 ;冷却后得到的催化剂碾磨至 200目的粉末 ;分批次称取适量的催化剂粉末分批次加入质量浓度为 25% 的NaOH 溶液中混合均匀,随后控制温度在 60℃反应 30min,反应完毕之后,用蒸馏水洗涤 3次、再用无水乙醇洗涤至中性;In this embodiment, the composition of the Raney nickel-aluminum-X catalyst used in the low-pressure reactor R1: the nickel-aluminum mass ratio is 0.7:1, and the amount of X added is 1wt% of the total mass of nickel-aluminum, where the X is Mg . The production process is as follows: Weigh 350kg of Ni block, 500kg of Al block and 8.5kg of Mg respectively in a medium and large furnace, turn on the current, wait until Ni, Al and Mg are melted, keep melting at 900°C for 60 minutes, then pour Cool in water; grind the catalyst obtained after cooling to a powder of 200 mesh; weigh an appropriate amount of catalyst powder in batches and add it to a NaOH solution with a mass concentration of 25% in batches, mix evenly, and then control the temperature at 60°C for 30 minutes to react. After completion, wash 3 times with distilled water and then wash with absolute ethanol until neutral;

冷冻水撤热列管式反应器R2所装填的催化剂组成:镍含量19 wt%,促进剂Cu含量5wt%,其余为氧化铝。该催化剂按下述步骤制备:取比表面为150 m2·g-1,孔容为1.3 cm3·g-1,平均孔径为20 nm的氧化铝载体76 Kg,取19.0 Kg三水合硝酸铜,配制成100 L溶液,将溶液浸渍到氧化铝载体中,静置30 min,后经110℃干燥10 h,400 ℃焙烧6 h后,得到含促进剂Cu的载体。将上述载体经150℃干燥10 h,后降至室温备用。称取49.5 Kg六水合硝酸镍、38.1 Kg四水合硝酸镍以及2 Kg CTAB,配制成130 L溶液,浸渍到上述含促进剂Cu的载体上,静置30 min,滤去剩余溶液;经100 ℃干燥8 h后,450 ℃焙烧6 h,然后通入氢气400 ℃还原5 h,还原后的催化剂经液体保护,备用。The composition of the catalyst packed in the chilled water heat removal tube reactor R2 is: nickel content 19 wt%, accelerator Cu content 5wt%, and the rest is alumina. The catalyst is prepared according to the following steps: take 76 Kg of alumina carrier with a specific surface of 150 m 2 ·g -1 , a pore volume of 1.3 cm 3 ·g -1 and an average pore diameter of 20 nm, and 19.0 Kg of copper nitrate trihydrate. , prepare a 100 L solution, immerse the solution into the alumina carrier, let it stand for 30 minutes, then dry at 110°C for 10 h, and roast at 400°C for 6 h to obtain a carrier containing accelerator Cu. The above carrier was dried at 150°C for 10 h, and then lowered to room temperature for use. Weigh 49.5 Kg of nickel nitrate hexahydrate, 38.1 Kg of nickel nitrate tetrahydrate and 2 Kg of CTAB, prepare a 130 L solution, dip it into the above carrier containing Cu as accelerator, let it stand for 30 minutes, filter out the remaining solution; After drying for 8 hours, it was calcined at 450°C for 6 hours, and then hydrogen was introduced at 400°C for reduction for 5 hours. The reduced catalyst was protected by liquid and is ready for use.

(1)经过加压至2.5MPa,40℃的35wt%的1,4-丁炔二醇水溶液进入低压反应器R1,保持反应压力控制在2.5MPa,并保持反应温度为60℃,调节反应液体空速为3h-1,加入氢气(99.99%)的压力为2.5 MPa,气体空速4 h-1,进行第一步加氢;产物经过减压后至0.4 MPa进入旋风分离器S1;旋风分离器S1底部分离出的雷尼-镍催化剂,顶部采出反应液,该反应液通过袋式过滤器S2进一步去除催化剂颗粒;从袋式过滤器S2分离出的催化剂和旋风分离器S1底部分离出的催化剂循环至低压反应器R1再次参加反应;(1) After pressurizing to 2.5MPa, a 35wt% 1,4-butynediol aqueous solution at 40°C enters the low-pressure reactor R1. Keep the reaction pressure at 2.5MPa and the reaction temperature at 60°C. Adjust the reaction liquid The space speed is 3h -1 , the pressure of adding hydrogen (99.99%) is 2.5 MPa, the gas space speed is 4 h -1 , and the first step of hydrogenation is carried out; the product enters the cyclone separator S1 after decompression to 0.4 MPa; cyclone separation The Raney-nickel catalyst separated from the bottom of the bag filter S1, the reaction liquid is taken out from the top, and the reaction liquid is further removed by the bag filter S2; the catalyst separated from the bag filter S2 is separated from the bottom of the cyclone separator S1 The catalyst is circulated to the low-pressure reactor R1 to participate in the reaction again;

(2)通过上述处理的反应液进入预分离塔T1,理论板数为4;在20KPa,操作温度保持在70℃。反应液被切分,水、丁醇、轻组分从塔顶馏出,重组分、1,4-丁二醇、1,4-丁烯二醇、羟基丁醛及缩醛的水溶液从塔底出来;(2) The reaction liquid after the above treatment enters the pre-separation tower T1, with a theoretical plate number of 4; at 20KPa, the operating temperature is maintained at 70°C. The reaction liquid is divided, water, butanol, and light components are distilled from the top of the tower, and the heavy components, 1,4-butanediol, 1,4-butenediol, hydroxybutyraldehyde and acetal aqueous solutions are distilled from the top of the tower. bottom out;

(3)从预分离塔T1顶部分离出的水、丁醇、轻组分进入下一分离工段提取副产品丁醇;(3) The water, butanol and light components separated from the top of the pre-separation tower T1 enter the next separation section to extract the by-product butanol;

(4)从预分离塔T1底部分离出的溶液通过加压和高压加氢预热器E1预热后加热至110℃、升压至25 MPa,从顶部以滴流方式进入冷冻水撤热列管式反应器R2中,反应温度控制在120℃;反应压力控制在25MPa;空速1.5h-1;进一步将少量的1,4-丁烯二醇、羟基丁醛及缩醛转化为1,4丁二醇,反应物从反应器底部采出。再经过蒸馏后得产品纯度为99.6%,色度等于3AHPA的1,4-丁二醇产品。动力电消耗395 千瓦时/吨1,4-丁二醇,蒸汽消耗 4.0 吨/吨1,4-丁二醇,循环冷却水消耗 295 吨/吨1,4-丁二醇。(4) The solution separated from the bottom of pre-separation tower T1 is preheated by pressurization and high-pressure hydrogenation preheater E1, heated to 110°C, raised to 25 MPa, and then enters the chilled water heat removal train in a trickle manner from the top In the tubular reactor R2, the reaction temperature is controlled at 120°C; the reaction pressure is controlled at 25MPa; the space velocity is 1.5h -1 ; a small amount of 1,4-butenediol, hydroxybutyraldehyde and acetal are further converted into 1, 4butanediol, the reactant is taken out from the bottom of the reactor. After further distillation, a 1,4-butanediol product with a purity of 99.6% and a color equal to 3AHPA is obtained. The power consumption is 395 kWh/ton of 1,4-butanediol, the steam consumption is 4.0 tons/ton of 1,4-butanediol, and the circulating cooling water consumption is 295 tons/ton of 1,4-butanediol.

实施例4Example 4

本实施例中,低压反应器R1所用的雷尼镍-铝-X催化剂组成:镍铝质量比为0.8:1,X 的添加量为镍铝总质量的1wt%,其中所述的X为Mg。制作过程如下:分别称取 400kg 的Ni 块,500kg 的 Al 块以及 9kg 的Mg置于中大型熔炉中,打开电流,待 Ni、Al及Mg熔化之后,在 900℃保温熔炼 60min 之后,倒入水中冷却;冷却后得到的催化剂碾磨至 200 目的粉末 ;分批次称取适量的催化剂粉末分批次加入质量浓度为 25% 的NaOH 溶液中混合均匀,随后控制温度在 60℃反应 30min,反应完毕之后,用蒸馏水洗涤 3次、再用无水乙醇洗涤至中性;In this example, the composition of the Raney nickel-aluminum-X catalyst used in the low-pressure reactor R1: the nickel-aluminum mass ratio is 0.8:1, and the amount of X added is 1wt% of the total mass of nickel-aluminum, where the X is Mg . The production process is as follows: Weigh 400kg of Ni block, 500kg of Al block and 9kg of Mg respectively and place them in a medium and large furnace. Turn on the current. After Ni, Al and Mg are melted, keep smelting at 900℃ for 60 minutes and then pour them into water. Cool; grind the catalyst obtained after cooling to a powder of 200 mesh; weigh an appropriate amount of catalyst powder in batches, add it to a NaOH solution with a mass concentration of 25% in batches, mix evenly, and then control the temperature at 60°C for 30 minutes to complete the reaction. Afterwards, wash 3 times with distilled water and then wash with absolute ethanol until neutral;

冷冻水撤热列管式反应器R2所装填的催化剂组成:镍含量22 wt%,促进剂Cu含量6wt%,其余为氧化铝。该催化剂按下述步骤制备:取比表面为150 m2·g-1,孔容为1.3 cm3·g-1,平均孔径为20 nm的氧化铝载体72 Kg,取22.8 Kg三水合硝酸铜,配制成100 L溶液,将溶液浸渍到氧化铝载体中,静置30 min,后经110℃干燥10 h,400 ℃焙烧6 h后,得到含促进剂Cu的载体。将上述载体经150℃干燥10 h,后降至室温备用。称取74.3 Kg六水合硝酸镍、29.7 Kg四水合硝酸镍以及2 Kg CTAB,配制成130 L溶液,浸渍到上述含促进剂Cu的载体上,静置30 min,滤去剩余溶液;经100 ℃干燥8 h后,450 ℃焙烧6 h,然后通入氢气400 ℃还原5 h,还原后的催化剂经液体保护,备用。The catalyst composition of the chilled water heat removal tube reactor R2 is: nickel content 22 wt%, accelerator Cu content 6wt%, and the rest is alumina. The catalyst is prepared according to the following steps: take 72 Kg of alumina carrier with a specific surface of 150 m 2 ·g -1 , a pore volume of 1.3 cm 3 ·g -1 and an average pore diameter of 20 nm, and 22.8 Kg of copper nitrate trihydrate. , prepare a 100 L solution, immerse the solution into the alumina carrier, let it stand for 30 minutes, then dry at 110°C for 10 h, and roast at 400°C for 6 h to obtain a carrier containing accelerator Cu. The above carrier was dried at 150°C for 10 h, and then lowered to room temperature for use. Weigh 74.3 Kg of nickel nitrate hexahydrate, 29.7 Kg of nickel nitrate tetrahydrate and 2 Kg of CTAB, prepare a 130 L solution, dip it into the above carrier containing Cu as accelerator, let it stand for 30 minutes, filter out the remaining solution; After drying for 8 hours, it was calcined at 450°C for 6 hours, and then hydrogen was introduced at 400°C for reduction for 5 hours. The reduced catalyst was protected by liquid and is ready for use.

(1)经过加压至2.0MPa,40℃的40wt%的1,4-丁炔二醇水溶液进入低压反应器R1,保持反应压力控制在2.0MPa,并保持反应温度为60℃,调节反应液体空速为4h-1,加入氢气(99.99%)的压力为2.0 MPa,气体空速2 h-1,进行第一步加氢;产物经过减压后至0.4 MPa进入旋风分离器S1;旋风分离器S1底部分离出的雷尼-镍催化剂,顶部采出反应液,该反应液通过袋式过滤器S2进一步去除催化剂颗粒;从袋式过滤器S2分离出的催化剂和旋风分离器S1底部分离出的催化剂循环至低压反应器R1再次参加反应;(1) After pressurizing to 2.0MPa, a 40wt% 1,4-butynediol aqueous solution at 40°C enters the low-pressure reactor R1. Keep the reaction pressure at 2.0MPa and the reaction temperature at 60°C. Adjust the reaction liquid The space speed is 4h -1 , the pressure of adding hydrogen (99.99%) is 2.0 MPa, the gas space speed is 2 h -1 , and the first step of hydrogenation is carried out; the product enters the cyclone separator S1 after decompression to 0.4 MPa; cyclone separation The Raney-nickel catalyst separated from the bottom of the bag filter S1, the reaction liquid is taken out from the top, and the reaction liquid is further removed by the bag filter S2; the catalyst separated from the bag filter S2 is separated from the bottom of the cyclone separator S1 The catalyst is circulated to the low-pressure reactor R1 to participate in the reaction again;

(2)通过上述处理的反应液进入预分离塔T1,理论板数为5;在15KPa,操作温度保持在75℃。反应液被切分,水、丁醇、轻组分从塔顶馏出,重组分、1,4-丁二醇、1,4-丁烯二醇、羟基丁醛及缩醛的水溶液从塔底出来;(2) The reaction liquid after the above treatment enters the pre-separation tower T1, with a theoretical plate number of 5; at 15KPa, the operating temperature is maintained at 75°C. The reaction liquid is divided, water, butanol, and light components are distilled from the top of the tower, and the heavy components, 1,4-butanediol, 1,4-butenediol, hydroxybutyraldehyde and acetal aqueous solutions are distilled from the top of the tower. bottom out;

(3)从预分离塔T1顶部分离出的水、丁醇、轻组分进入下一分离工段提取副产品丁醇;(3) The water, butanol and light components separated from the top of the pre-separation tower T1 enter the next separation section to extract the by-product butanol;

(4)从预分离塔T1底部分离出的溶液通过加压和高压加氢预热器E1预热后加热至120℃、升压至25 MPa,从顶部以滴流方式进入冷冻水撤热列管式反应器R2中,反应温度控制在130℃;反应压力控制在25MPa;空速1.5h-1;进一步将少量的1,4-丁烯二醇、羟基丁醛及缩醛转化为1,4丁二醇,反应物从反应器底R2部采出。再经过蒸馏后得产品纯度为99.7%,色度等于2AHPA的1,4-丁二醇产品。动力电消耗400 千瓦时/吨1,4-丁二醇,蒸汽消耗 4.1吨/吨1,4-丁二醇,循环冷却水消耗 300 吨/吨1,4-丁二醇。(4) The solution separated from the bottom of pre-separation tower T1 is preheated by pressurization and high-pressure hydrogenation preheater E1, heated to 120°C, raised to 25 MPa, and enters the chilled water heat removal train in a trickle manner from the top In the tubular reactor R2, the reaction temperature is controlled at 130°C; the reaction pressure is controlled at 25MPa; the space velocity is 1.5h -1 ; a small amount of 1,4-butenediol, hydroxybutyraldehyde and acetal are further converted into 1, 4 butanediol, the reactant is taken out from the R2 part at the bottom of the reactor. After further distillation, a 1,4-butanediol product with a purity of 99.7% and a color equal to 2AHPA is obtained. Power electricity consumption is 400 kWh/ton of 1,4-butanediol, steam consumption is 4.1 tons/ton of 1,4-butanediol, and circulating cooling water consumption is 300 tons/ton of 1,4-butanediol.

实施例5Example 5

本实施例中,低压反应器R1所用的雷尼镍-铝-X催化剂组成:镍铝质量比为1:1,X的添加量为镍铝总质量的2wt%,其中所述的X为Mg。制作过程如下:分别称取 400kg 的 Ni块,500kg 的 Al 块以及 9kg 的Mg置于中大型熔炉中,打开电流,待 Ni、Al及Mg熔化之后,在 900℃保温熔炼 60min 之后,倒入水中冷却;冷却后得到的催化剂碾磨至 200 目的粉末 ;分批次称取适量的催化剂粉末分批次加入质量浓度为 25% 的NaOH 溶液中混合均匀,随后控制温度在 60℃反应 30min,反应完毕之后,用蒸馏水洗涤 3次、再用无水乙醇洗涤至中性;In this example, the composition of the Raney nickel-aluminum-X catalyst used in the low-pressure reactor R1: the mass ratio of nickel to aluminum is 1:1, and the amount of X added is 2wt% of the total mass of nickel and aluminum, where the X is Mg . The production process is as follows: Weigh 400kg of Ni block, 500kg of Al block and 9kg of Mg respectively in a medium and large furnace, turn on the current, wait until Ni, Al and Mg are melted, then keep smelting at 900℃ for 60 minutes, then pour into water Cool; grind the catalyst obtained after cooling to a powder of 200 mesh; weigh an appropriate amount of catalyst powder in batches, add it to a NaOH solution with a mass concentration of 25% in batches, mix evenly, and then control the temperature at 60°C for 30 minutes to complete the reaction. Afterwards, wash 3 times with distilled water and then wash with absolute ethanol until neutral;

冷冻水撤热列管式反应器R2所装填的催化剂组成:镍含量22 wt%,促进剂Cu含量6wt%,其余为氧化铝。该催化剂按下述步骤制备:取比表面为150 m2·g-1,孔容为1.3 cm3·g-1,平均孔径为20 nm的氧化铝载体72 Kg,取22.8 Kg三水合硝酸铜,配制成100 L溶液,将溶液浸渍到氧化铝载体中,静置30 min,后经110℃干燥10 h,400 ℃焙烧6 h后,得到含促进剂Cu的载体。将上述载体经150℃干燥10 h,后降至室温备用。称取74.3 Kg六水合硝酸镍、29.7 Kg四水合硝酸镍以及2 Kg CTAB,配制成130 L溶液,浸渍到上述含促进剂Cu的载体上,静置30 min,滤去剩余溶液;经100 ℃干燥8 h后,450 ℃焙烧6 h,然后通入氢气400 ℃还原5 h,还原后的催化剂经液体保护,备用。The catalyst composition of the chilled water heat removal tube reactor R2 is: nickel content 22 wt%, accelerator Cu content 6wt%, and the rest is alumina. The catalyst is prepared according to the following steps: take 72 Kg of alumina carrier with a specific surface of 150 m 2 ·g -1 , a pore volume of 1.3 cm 3 ·g -1 and an average pore diameter of 20 nm, and 22.8 Kg of copper nitrate trihydrate. , prepare a 100 L solution, immerse the solution into the alumina carrier, let it stand for 30 minutes, then dry at 110°C for 10 h, and roast at 400°C for 6 h to obtain a carrier containing accelerator Cu. The above carrier was dried at 150°C for 10 h, and then lowered to room temperature for use. Weigh 74.3 Kg of nickel nitrate hexahydrate, 29.7 Kg of nickel nitrate tetrahydrate and 2 Kg of CTAB, prepare a 130 L solution, dip it into the above carrier containing Cu as accelerator, let it stand for 30 minutes, filter out the remaining solution; After drying for 8 hours, it was calcined at 450°C for 6 hours, and then hydrogen was introduced at 400°C for reduction for 5 hours. The reduced catalyst was protected by liquid and is ready for use.

(1)经过加压至1.1MPa,45℃的40wt%的1,4-丁炔二醇水溶液进入低压反应器R1,保持反应压力控制在1.1 MPa,并保持反应温度为75℃,调节反应液体空速为4h-1,加入氢气(99.99%)的压力为1.1 MPa,气体空速1.5 h-1,进行第一步加氢;产物经过减压后至0.8MPa进入旋风分离器S1;旋风分离器S1底部分离出的雷尼-镍催化剂,顶部采出反应液,该反应液通过袋式过滤器S2进一步去除催化剂颗粒;从袋式过滤器S2分离出的催化剂和旋风分离器S1底部分离出的催化剂循环至低压反应器R1再次参加反应;(1) After pressurizing to 1.1MPa, a 40wt% 1,4-butynediol aqueous solution at 45°C enters the low-pressure reactor R1. Keep the reaction pressure at 1.1 MPa and the reaction temperature at 75°C. Adjust the reaction liquid The space speed is 4h -1 , the pressure of adding hydrogen (99.99%) is 1.1 MPa, the gas space speed is 1.5 h -1 , and the first step of hydrogenation is carried out; the product enters the cyclone separator S1 after decompression to 0.8MPa; cyclone separation The Raney-nickel catalyst separated from the bottom of the bag filter S1, the reaction liquid is taken out from the top, and the reaction liquid is further removed by the bag filter S2; the catalyst separated from the bag filter S2 is separated from the bottom of the cyclone separator S1 The catalyst is circulated to the low-pressure reactor R1 to participate in the reaction again;

(2)通过上述处理的反应液进入预分离塔T1,理论板数为3;在25KPa,操作温度保持在60℃。反应液被切分,水、丁醇、轻组分从塔顶馏出,重组分、1,4-丁二醇、1,4-丁烯二醇、羟基丁醛及缩醛的水溶液从塔底出来;(2) The reaction liquid after the above treatment enters the pre-separation tower T1, with a theoretical plate number of 3; at 25KPa, the operating temperature is maintained at 60°C. The reaction liquid is divided, water, butanol, and light components are distilled from the top of the tower, and the heavy components, 1,4-butanediol, 1,4-butenediol, hydroxybutyraldehyde and acetal aqueous solutions are distilled from the top of the tower. bottom out;

(3)从预分离塔T1顶部分离出的水、丁醇、轻组分进入下一分离工段提取副产品丁醇;(3) The water, butanol and light components separated from the top of the pre-separation tower T1 enter the next separation section to extract the by-product butanol;

(4)从预分离塔T1底部分离出的溶液通过加压和高压加氢预热器E1预热后加热至95℃、升压至10 MPa,从顶部以滴流方式进入冷冻水撤热列管式反应器R2中,反应温度控制在95℃;反应压力控制在10MPa;空速2.5h-1;进一步将少量的1,4-丁烯二醇、羟基丁醛及缩醛转化为1,4丁二醇,反应物从反应器底R2部采出。再经过蒸馏后得产品纯度为99.7%,色度等于2AHPA的1,4-丁二醇产品。动力电消耗380 千瓦时/吨1,4-丁二醇,蒸汽消耗 3.8 吨/吨1,4-丁二醇,循环冷却水消耗 290 吨/吨1,4-丁二醇。(4) The solution separated from the bottom of pre-separation tower T1 is preheated by pressurization and high-pressure hydrogenation preheater E1, heated to 95°C, raised to 10 MPa, and then enters the chilled water heat removal train in a trickle manner from the top In the tubular reactor R2, the reaction temperature is controlled at 95°C; the reaction pressure is controlled at 10MPa; the space velocity is 2.5h -1 ; a small amount of 1,4-butenediol, hydroxybutyraldehyde and acetal are further converted into 1, 4 butanediol, the reactant is taken out from the R2 part at the bottom of the reactor. After further distillation, a 1,4-butanediol product with a purity of 99.7% and a color equal to 2AHPA is obtained. The power consumption is 380 kWh/ton of 1,4-butanediol, the steam consumption is 3.8 tons/ton of 1,4-butanediol, and the circulating cooling water consumption is 290 tons/ton of 1,4-butanediol.

实施例6Example 6

本实施例中,低压反应器R1所用的雷尼镍-铝-X催化剂组成:镍铝质量比为0.8:1,X 的添加量为镍铝总质量的1wt%,其中所述的X为Mg。制作过程如下:分别称取 400kg 的Ni 块,500kg 的 Al 块以及 9kg 的Mg置于中大型熔炉中,打开电流,待 Ni、Al及Mg熔化之后,在 900℃保温熔炼 60min 之后,倒入水中冷却;冷却后得到的催化剂碾磨至 200 目的粉末 ;分批次称取适量的催化剂粉末分批次加入质量浓度为 25% 的NaOH 溶液中混合均匀,随后控制温度在 60℃反应 30min,反应完毕之后,用蒸馏水洗涤 3次、再用无水乙醇洗涤至中性;In this example, the composition of the Raney nickel-aluminum-X catalyst used in the low-pressure reactor R1: the nickel-aluminum mass ratio is 0.8:1, and the amount of X added is 1wt% of the total mass of nickel-aluminum, where the X is Mg . The production process is as follows: Weigh 400kg of Ni block, 500kg of Al block and 9kg of Mg respectively and place them in a medium and large furnace. Turn on the current. After Ni, Al and Mg are melted, keep smelting at 900℃ for 60 minutes and then pour them into water. Cool; grind the catalyst obtained after cooling to a powder of 200 mesh; weigh an appropriate amount of catalyst powder in batches, add it to a NaOH solution with a mass concentration of 25% in batches, mix evenly, and then control the temperature at 60°C for 30 minutes to complete the reaction. Afterwards, wash 3 times with distilled water and then wash with absolute ethanol until neutral;

冷冻水撤热列管式反应器R2所装填的催化剂组成:镍含量22 wt%,促进剂Cu含量6wt%,其余为氧化铝。该催化剂按下述步骤制备:取比表面为150 m2·g-1,孔容为1.3 cm3·g-1,平均孔径为20 nm的氧化铝载体72 Kg,取22.8 Kg三水合硝酸铜,配制成100 L溶液,将溶液浸渍到氧化铝载体中,静置30 min,后经110℃干燥10 h,400 ℃焙烧6 h后,得到含促进剂Cu的载体。将上述载体经150℃干燥10 h,后降至室温备用。称取74.3 Kg六水合硝酸镍、29.7 Kg四水合硝酸镍以及2 Kg CTAB,配制成130 L溶液,浸渍到上述含促进剂Cu的载体上,静置30 min,滤去剩余溶液;经100 ℃干燥8 h后,450 ℃焙烧6 h,然后通入氢气400 ℃还原5 h,还原后的催化剂经液体保护,备用。The catalyst composition of the chilled water heat removal tube reactor R2 is: nickel content 22 wt%, accelerator Cu content 6wt%, and the rest is alumina. The catalyst is prepared according to the following steps: take 72 Kg of alumina carrier with a specific surface of 150 m 2 ·g -1 , a pore volume of 1.3 cm 3 ·g -1 and an average pore diameter of 20 nm, and 22.8 Kg of copper nitrate trihydrate. , prepare a 100 L solution, immerse the solution into the alumina carrier, let it stand for 30 minutes, then dry at 110°C for 10 h, and roast at 400°C for 6 h to obtain a carrier containing accelerator Cu. The above carrier was dried at 150°C for 10 h, and then lowered to room temperature for use. Weigh 74.3 Kg of nickel nitrate hexahydrate, 29.7 Kg of nickel nitrate tetrahydrate and 2 Kg of CTAB, prepare a 130 L solution, dip it into the above carrier containing Cu as accelerator, let it stand for 30 minutes, filter out the remaining solution; After drying for 8 hours, it was calcined at 450°C for 6 hours, and then hydrogen was introduced at 400°C for reduction for 5 hours. The reduced catalyst was protected by liquid and is ready for use.

(1)经过加压至2.0MPa,40℃的40wt%的1,4-丁炔二醇水溶液进入低压反应器R1,保持反应压力控制在2.0MPa,并保持反应温度为60℃,调节反应液体空速为4h-1,加入氢气(99.99%)的压力为2.0 MPa,气体空速11 h-1,进行第一步加氢;产物经过减压后至0.4 MPa进入旋风分离器S1;旋风分离器S1底部分离出的雷尼-镍催化剂,顶部采出反应液,该反应液通过袋式过滤器S2进一步去除催化剂颗粒;从袋式过滤器S2分离出的催化剂和旋风分离器S1底部分离出的催化剂循环至低压反应器R1再次参加反应;(1) After pressurizing to 2.0MPa, a 40wt% 1,4-butynediol aqueous solution at 40°C enters the low-pressure reactor R1. Keep the reaction pressure at 2.0MPa and the reaction temperature at 60°C. Adjust the reaction liquid The space speed is 4h -1 , the pressure of adding hydrogen (99.99%) is 2.0 MPa, the gas space speed is 11 h -1 , and the first step of hydrogenation is carried out; the product enters the cyclone separator S1 after decompression to 0.4 MPa; cyclone separation The Raney-nickel catalyst separated from the bottom of the bag filter S1, the reaction liquid is taken out from the top, and the reaction liquid is further removed by the bag filter S2; the catalyst separated from the bag filter S2 is separated from the bottom of the cyclone separator S1 The catalyst is circulated to the low-pressure reactor R1 to participate in the reaction again;

(2)通过上述处理的反应液进入预分离塔T1,理论板数为5;在15KPa,操作温度保持在75℃。反应液被切分,水、丁醇、轻组分从塔顶馏出,重组分、1,4-丁二醇、1,4-丁烯二醇、羟基丁醛及缩醛的水溶液从塔底出来;(2) The reaction liquid after the above treatment enters the pre-separation tower T1, with a theoretical plate number of 5; at 15KPa, the operating temperature is maintained at 75°C. The reaction liquid is divided, water, butanol, and light components are distilled from the top of the tower, and the heavy components, 1,4-butanediol, 1,4-butenediol, hydroxybutyraldehyde and acetal aqueous solutions are distilled from the top of the tower. bottom out;

(3)从预分离塔T1顶部分离出的水、丁醇、轻组分进入下一分离工段提取副产品丁醇;(3) The water, butanol and light components separated from the top of the pre-separation tower T1 enter the next separation section to extract the by-product butanol;

(4)从预分离塔T1底部分离出的溶液通过加压和高压加氢预热器E1预热后加热至140℃、升压至30 MPa,从顶部以滴流方式进入冷冻水撤热列管式反应器R2中,反应温度控制在140℃;反应压力控制在30MPa;空速0.5h-1;进一步将少量的1,4-丁烯二醇、羟基丁醛及缩醛转化为1,4丁二醇,反应物从反应器底R2部采出。再经过蒸馏后得产品纯度为99.7%,色度等于2AHPA的1,4-丁二醇产品。动力电消耗420 千瓦时/吨1,4-丁二醇,蒸汽消耗 4.5吨/吨1,4-丁二醇,循环冷却水消耗 320 吨/吨1,4-丁二醇。(4) The solution separated from the bottom of pre-separation tower T1 is preheated by pressurization and high-pressure hydrogenation preheater E1, heated to 140°C, raised to 30 MPa, and enters the chilled water heat removal train in a trickle manner from the top In the tubular reactor R2, the reaction temperature is controlled at 140°C; the reaction pressure is controlled at 30MPa; the space velocity is 0.5h -1 ; a small amount of 1,4-butenediol, hydroxybutyraldehyde and acetal are further converted into 1, 4 butanediol, the reactant is taken out from the R2 part at the bottom of the reactor. After further distillation, a 1,4-butanediol product with a purity of 99.7% and a color equal to 2AHPA is obtained. The power consumption is 420 kWh/ton of 1,4-butanediol, the steam consumption is 4.5 tons/ton of 1,4-butanediol, and the circulating cooling water consumption is 320 tons/ton of 1,4-butanediol.

Claims (6)

1.一种1,4-丁炔二醇加氢制1,4-丁二醇的方法,其特征在于,包括:1. A method for hydrogenating 1,4-butynediol to produce 1,4-butanediol, which is characterized by comprising: 步骤一,经过加压的30wt%~40wt%的1,4-丁炔二醇水溶液进入低压反应器,在雷尼镍-铝-X催化剂作用下,进行第一步加氢反应,产物经过减压后进入常压的旋风分离器,分离器底部分离出雷尼镍-铝-X催化剂,顶部采出反应液,反应液通过袋式过滤器进一步去除催化剂颗粒;所述雷尼镍-铝-X催化剂中 X 为Mg、B、Sr、Cr、S、Ti、La、Sn、W、Mo、Fe 中的任意一种;Step 1: Pressurized 30wt% to 40wt% 1,4-butynediol aqueous solution enters the low-pressure reactor, and under the action of Raney Nickel-Aluminum-X catalyst, the first step of hydrogenation reaction is carried out, and the product is reduced After being pressed, it enters a cyclone separator at normal pressure. The Raney Nickel-Aluminum-X catalyst is separated from the bottom of the separator, and the reaction liquid is taken out from the top. The reaction liquid passes through a bag filter to further remove the catalyst particles; the Raney Nickel-Aluminum- In the X catalyst, X is any one of Mg, B, Sr, Cr, S, Ti, La, Sn, W, Mo, and Fe; 步骤二,反应液进入预分离塔;在真空状态下反应液被切分,水、正丁醇、轻组分从塔顶馏出,从塔底出来含有1,4-丁二醇、1,4-丁烯二醇、羟基丁醛、缩醛和重组分的混合水溶液;所述的预分离塔,其理论板数为3~5,操作压力为15KPa~25KPa;操作温度为60℃~75℃;In step two, the reaction liquid enters the pre-separation tower; the reaction liquid is cut under vacuum, water, n-butanol, and light components are distilled from the top of the tower, and the bottom of the tower contains 1,4-butanediol, 1, A mixed aqueous solution of 4-butenediol, hydroxybutyraldehyde, acetal and heavy components; the pre-separation tower has a theoretical plate number of 3 to 5, an operating pressure of 15KPa to 25KPa, and an operating temperature of 60°C to 75 ℃; 步骤三,从预分离塔顶部分离出的水、正丁醇、轻组分进入下一分离工段提取副产品正丁醇;Step 3: The water, n-butanol and light components separated from the top of the pre-separation tower enter the next separation section to extract the by-product n-butanol; 步骤四,从预分离塔底部分离出的混合水溶液通过加压和高压加氢预热器预热后进入冷冻水撤热列管式反应器中,反应温度控制在95℃~140℃;反应压力控制在10.0~30.0MPa; 反应器液体空速0.5~2.5h-1;冷冻水撤热列管式反应器中所装填催化剂的组成为:镍含量11-22 wt%,促进剂含量1~6 wt%,其余为氧化铝,所述的促进剂是镧、铜、镁元素中的一种;将1,4-丁烯二醇、羟基丁醛及缩醛在催化剂作用下转化为1,4-丁二醇,反应物从反应器底部采出,再经过蒸馏后得1,4-丁二醇产品。Step 4: The mixed aqueous solution separated from the bottom of the pre-separation tower is preheated by pressurization and high-pressure hydrogenation preheater and then enters the chilled water heat removal tube reactor. The reaction temperature is controlled between 95°C and 140°C; the reaction pressure Controlled at 10.0~30.0MPa; reactor liquid space velocity 0.5~2.5h -1 ; the composition of the catalyst loaded in the chilled water heat removal tubular reactor is: nickel content 11-22 wt%, accelerator content 1~6 wt%, the rest is alumina, the accelerator is one of lanthanum, copper, and magnesium; 1,4-butenediol, hydroxybutyraldehyde and acetal are converted into 1,4 under the action of the catalyst -Butanediol, the reactant is taken out from the bottom of the reactor, and then distilled to obtain the 1,4-butanediol product. 2.根据权利要求1所述的1,4-丁炔二醇加氢制1,4-丁二醇的方法,其特征在于:步骤一中,低压反应器中所用的雷尼镍-铝-X催化剂由组成为镍铝质量比为(0.5-1):1,X 的添加量为镍铝总质量的1wt%-2wt %。2. The method for hydrogenating 1,4-butynediol to produce 1,4-butanediol according to claim 1, characterized in that: in step one, the Raney nickel-aluminum- The composition of the X catalyst is that the mass ratio of nickel to aluminum is (0.5-1): 1, and the amount of X added is 1wt%-2wt% of the total mass of nickel and aluminum. 3.根据权利要求1或2所述的1,4-丁炔二醇加氢制1,4-丁二醇的方法,其特征在于:步骤一中,低压反应器进口溶液为30wt%~40wt%的1,4-丁炔二醇水溶液,入口温度为40℃~45℃,入口压力为1.1~4.1MPa,液体空速为1~4h-1;入口气体为99.99wt%的氢气,入口压力为1.1~4.1MPa,气体空速为1.5~11 h-1;液体出口压力为0.4~0.8MPa,出口温度为60℃~75℃。3. The method for hydrogenating 1,4-butynediol to produce 1,4-butanediol according to claim 1 or 2, characterized in that: in step one, the low-pressure reactor inlet solution is 30wt% ~ 40wt % of 1,4-butynediol aqueous solution, the inlet temperature is 40℃~45℃, the inlet pressure is 1.1~4.1MPa, the liquid space velocity is 1~4h -1 ; the inlet gas is 99.99wt% hydrogen, the inlet pressure It is 1.1~4.1MPa, the gas space velocity is 1.5~11 h -1 ; the liquid outlet pressure is 0.4~0.8MPa, and the outlet temperature is 60℃~75℃. 4.根据权利要求3所述的1,4-丁炔二醇加氢制1,4-丁二醇的方法,其特征在于:低压反应器为带有夹套撤热系统的淤浆床反应器。4. The method for hydrogenating 1,4-butynediol to produce 1,4-butanediol according to claim 3, characterized in that: the low-pressure reactor is a slurry bed reaction with a jacketed heat removal system. device. 5.根据权利要求4所述的1,4-丁炔二醇加氢制1,4-丁二醇的方法,其特征在于:步骤四中,所述的高压加氢预热器为管壳式换热器,液体入口温度为60℃~75℃,出口温度为95℃~140℃。5. The method for hydrogenating 1,4-butynediol to produce 1,4-butanediol according to claim 4, characterized in that: in step four, the high-pressure hydrogenation preheater is a tube shell Type heat exchanger, the liquid inlet temperature is 60℃~75℃, and the outlet temperature is 95℃~140℃. 6.根据权利要求1所述的1,4-丁炔二醇加氢制1,4-丁二醇的方法,其特征在于:从袋式过滤器分离出的催化剂和旋风分离器底部分离出的催化剂循环至低压反应器再次参加反应。6. The method for hydrogenating 1,4-butynediol to produce 1,4-butanediol according to claim 1, characterized in that: the catalyst separated from the bag filter and the bottom of the cyclone separator are separated The catalyst is circulated to the low-pressure reactor to participate in the reaction again.
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Publication number Priority date Publication date Assignee Title
CN116474783A (en) * 2023-02-24 2023-07-25 伊犁师范大学 Ni-La/Al for preparing 1, 4-butanediol by catalytic hydrogenation of 1, 4-butynediol 2 O 3 Catalyst

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3449445A (en) * 1967-03-17 1969-06-10 Gaf Corp Process of preparing 1,4-butanediol
CN1081174A (en) * 1992-07-08 1994-01-26 化学工业部北京化工研究院 Butynediol medium-pressure hydrocracking system butyleneglycol Process
CN101306368A (en) * 2008-07-09 2008-11-19 山西大学 Preparation method of butynediol two-step hydrogenation to butanediol two-stage hydrogenation catalyst
CN102744083A (en) * 2012-06-26 2012-10-24 华烁科技股份有限公司 Preparation method and activation method of Raney nickel-aluminum-X catalyst specially for hydrogenation preparation of 1,4-butanediol from 1,4-butynediol
CN106397129A (en) * 2016-11-24 2017-02-15 查都(上海)科技有限公司 System and process for continuously producing 2-butene-1,4-diol and co-producing 1,4-butanediol through hydrogenation of 1,4-butynediol
WO2017042289A1 (en) * 2015-09-10 2017-03-16 Shell Internationale Research Maatschappij B.V. Process for the production of 1,4-butanediol and tetrahydrofuran from furan
KR20170065933A (en) * 2015-12-04 2017-06-14 서강대학교산학협력단 Method and product for purifying alcohol
CN107141196A (en) * 2017-06-27 2017-09-08 查都(上海)科技有限公司 A kind of 1,4 butynediols two-stage hydrogenation systems
CN107778138A (en) * 2016-08-30 2018-03-09 中国石油化工股份有限公司 A kind of method that Isosorbide-5-Nitrae butynediols two-stage hydrogenation prepares Isosorbide-5-Nitrae butanediol
WO2018157684A1 (en) * 2017-02-28 2018-09-07 山西大学 Ni-coated al2o3@sio2 catalyst, preparation method thereof and application thereof

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3449445A (en) * 1967-03-17 1969-06-10 Gaf Corp Process of preparing 1,4-butanediol
CN1081174A (en) * 1992-07-08 1994-01-26 化学工业部北京化工研究院 Butynediol medium-pressure hydrocracking system butyleneglycol Process
CN101306368A (en) * 2008-07-09 2008-11-19 山西大学 Preparation method of butynediol two-step hydrogenation to butanediol two-stage hydrogenation catalyst
CN102744083A (en) * 2012-06-26 2012-10-24 华烁科技股份有限公司 Preparation method and activation method of Raney nickel-aluminum-X catalyst specially for hydrogenation preparation of 1,4-butanediol from 1,4-butynediol
WO2017042289A1 (en) * 2015-09-10 2017-03-16 Shell Internationale Research Maatschappij B.V. Process for the production of 1,4-butanediol and tetrahydrofuran from furan
KR20170065933A (en) * 2015-12-04 2017-06-14 서강대학교산학협력단 Method and product for purifying alcohol
CN107778138A (en) * 2016-08-30 2018-03-09 中国石油化工股份有限公司 A kind of method that Isosorbide-5-Nitrae butynediols two-stage hydrogenation prepares Isosorbide-5-Nitrae butanediol
CN106397129A (en) * 2016-11-24 2017-02-15 查都(上海)科技有限公司 System and process for continuously producing 2-butene-1,4-diol and co-producing 1,4-butanediol through hydrogenation of 1,4-butynediol
WO2018157684A1 (en) * 2017-02-28 2018-09-07 山西大学 Ni-coated al2o3@sio2 catalyst, preparation method thereof and application thereof
CN107141196A (en) * 2017-06-27 2017-09-08 查都(上海)科技有限公司 A kind of 1,4 butynediols two-stage hydrogenation systems

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Ni/Al_2O_3催化剂的制备及丁炔二醇加氢反应的研究;张建平;李海涛;高春光;赵永祥;;山西大学学报(自然科学版)(第03期);413-417 *

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