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順酐法BDO，顧名思義是以順酐為原料制備BDO的工藝，其原料順酐可由苯或者丁烷氧化制成。由于環(huán)境污染問題，國內(nèi)苯法順酐裝置長期處于停產(chǎn)狀態(tài)或者經(jīng)過改造以丁烷氧化制順酐，目前全球80%順酐產(chǎn)能都采用固定床丁烷法，具有原料易得、污染小、產(chǎn)品收率高等特點。

The maleic anhydride method BDO, as the name suggests, is a process of preparing BDO from maleic anhydride, which can be made by oxidation of benzene or butane. Due to environmental pollution issues, the domestic benzene based maleic anhydride plant has been in a long-term shutdown state or has undergone transformation to produce maleic anhydride through butane oxidation. Currently, 80% of the global maleic anhydride production capacity adopts the fixed bed butane method, which has the characteristics of easy access to raw materials, low pollution, and high product yield.

順酐法，根據(jù)順酐加氫時的步驟不同可分為直接加氫法與間接加氫法，間接加氫法中根據(jù)加氫時的物料形態(tài)又可分為氣相加氫法與液相加氫法。

The maleic anhydride method can be divided into direct hydrogenation method and indirect hydrogenation method based on the different steps of maleic anhydride hydrogenation. In the indirect hydrogenation method, it can be further divided into gas-phase hydrogenation method and liquid-phase hydrogenation method based on the material morphology during hydrogenation.

直接加氫與間接加氫

Direct hydrogenation and indirect hydrogenation

直接加氫法

Direct hydrogenation method

順酐直接加氫工藝是20世紀(jì)60年代早由三菱油化以及三菱化成公司聯(lián)合開發(fā)成功的。該工藝能夠同時不同比例的THF (四氫呋喃)、GBL (y-丁內(nèi)酯)和BDO等系列產(chǎn)品，反應(yīng)條件不同，其產(chǎn)品的相應(yīng)組成也是不同的。

The direct hydrogenation process of maleic anhydride was first successfully developed by Mitsubishi Oil and Chemical Corporation in the 1960s. This process can simultaneously produce series products such as THF (tetrahydrofuran), GBL (y-butyrolactone), and BDO in different proportions. The corresponding composition of the products varies depending on the reaction conditions.

酯化加氫法

Esterification hydrogenation method

間接酯化加氫工藝早是由英國Davy公司開發(fā)成功的，因此又叫Davy法。加氫反應(yīng)可以在氣相或者是液相中進(jìn)行，采用了銅系催化劑，主體反應(yīng)的條件要比順酐直接加氫工藝溫和很多。

The indirect esterification hydrogenation process was first developed by Davy Company in the UK, hence it is also known as the Davy method. Hydrogenation reactions can be carried out in gas or liquid phases, using copper based catalysts. The main reaction conditions are much milder than those of direct hydrogenation of maleic anhydride.

由于順酐加氫是強放熱反應(yīng)，直接加氫反應(yīng)條件苛刻，控制難度高，目前還沒有工業(yè)化運行裝置，在運裝置均采用的是間接法。

Due to the strong exothermic reaction of maleic anhydride hydrogenation, the direct hydrogenation reaction conditions are harsh and difficult to control. Currently, there is no industrial operation device, and the indirect method is used in the operating devices.

氣相加氫與液相加氫

Gas phase hydrogenation and liquid phase hydrogenation

兩者化學(xué)反應(yīng)方程式是一致的，區(qū)別在于加氫單元馬來酸二甲酯是在氣相還是在液相條件下反應(yīng)。

The chemical reaction equations of the two are consistent, with the difference being whether the hydrogenation unit dimethyl maleate reacts under gas or liquid phase conditions.

氣相加氫順酐法，是在進(jìn)行加氫反應(yīng)時，將所有的物料先氣化為氣相，再與氫氣（同樣為氣相）反應(yīng)，終制得BDO，并副產(chǎn)少量THF（根據(jù)需要也可以副產(chǎn)少量GBL）。

The gas-phase hydrogenation maleic anhydride method is a hydrogenation reaction in which all materials are first gasified into the gas phase, and then reacted with hydrogen gas (also in the gas phase) to finally produce BDO, with a small amount of THF produced as a byproduct (a small amount of GBL can also be produced as needed).

以意大利Conser為代表的液相加氫順酐法，則不需要進(jìn)化步驟，而是直接將液相的物料與氫氣（氣相）反應(yīng)制BDO，因此該方法又可稱為混合相加氫順酐法。

The liquid-phase hydrogenation maleic anhydride method, represented by the Italian Conser, does not require gasification steps, but directly reacts the liquid-phase material with hydrogen (gas phase) to produce BDO. Therefore, this method can also be called the mixed phase hydrogenation maleic anhydride method.

目前多數(shù)技術(shù)公司的工藝是氣相加氫工藝。

At present, most technology companies use gas-phase hydrogenation technology.

消耗與排放

Consumption and emissions

正丁烷順酐法制BDO工藝路線，噸BDO的主要消耗大致為正丁烷1.15t、氫氣1200 m3。該法的主要原料為正丁烷和氫氣，正丁烷的按5000元/t計算，BDO的原料成本約1. 05萬元/t；如果外購順酐BDO，目前順酐的市場價約為1. 2萬元/t，噸BDO消耗順酐1.12t左右，BDO的成本較高。

The BDO process route using n-butane maleic anhydride produces approximately 1.15 tons of n-butane and 1200 m3 of hydrogen gas per ton of BDO. The main raw materials for this method are n-butane and hydrogen gas. The price of n-butane is calculated at 5000 yuan/t, and the raw material cost for producing BDO is about 1 050000 yuan/t; If purchasing maleic anhydride to produce BDO, the current market price of maleic anhydride is about 1 20000 yuan/t, with a consumption of about 1.12 tons of maleic anhydride per ton of BDO, the production cost of BDO is relatively high.

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