ZZ-PRO脫硫工藝

超重力技術(shù)簡(jiǎn)介

  1976年,美國(guó)太空署(NASA)征求微重力場(chǎng)實(shí)驗(yàn)項(xiàng)目,英國(guó)ICI公司(帝國(guó)化學(xué)工業(yè)公司)提出了超重力分離技術(shù),發(fā)現(xiàn)在超重力環(huán)境下,單元操作的傳質(zhì)效率能夠強(qiáng)化百倍特征,由此提出了超重力技術(shù)。

  超重力技術(shù)是利用比地球重力加速度大得多的超重力環(huán)境對(duì)“三傳一反”過(guò)程進(jìn)行強(qiáng)化的新技術(shù),在地球上通過(guò)旋轉(zhuǎn)產(chǎn)生模擬的超重力環(huán)境而獲得。它能夠大幅度提高反應(yīng)的轉(zhuǎn)化率和選擇性,顯著地縮小反應(yīng)器的體積,簡(jiǎn)化工藝、流程,實(shí)現(xiàn)過(guò)程的高效節(jié)能,減少污染排放。研究和分析表明,在超重力環(huán)境下,相間傳質(zhì)速率比傳統(tǒng)的塔器中提高1-3個(gè)數(shù)量級(jí),這樣我們可以將高達(dá)幾十米的巨大化工塔設(shè)備用高不及幾米的超重力機(jī)進(jìn)行替代。因此,超重力工程技術(shù)被認(rèn)為是強(qiáng)化傳遞和多相反應(yīng)過(guò)程的一項(xiàng)突破性技術(shù),被譽(yù)為跨世紀(jì)的技術(shù),超重力機(jī)也被譽(yù)為“化學(xué)工業(yè)的晶體管”。

Introduction to supergravity technology

In 1976, the United States Space Agency (NASA) solicited the microgravity field experiment project, and the British ICI Company (Imperial Chemical Industries Company) proposed the super-gravity separation technology, which found that in the super-gravity environment, the mass transfer efficiency of the unit operation can strengthen the characteristics of a hundred times, which proposed the super-gravity technology.

Supergravity technology is a new technology to strengthen the "three pass and one reverse" process by using a supergravity environment that is much larger than the Earth's gravity acceleration, and it is obtained by rotating the simulated supergravity environment on the Earth. It can greatly improve the conversion rate and selectivity of the reaction, significantly reduce the volume of the reactor, simplify the process and flow, achieve high efficiency and energy saving of the process, and reduce pollution emission. Research and analysis show that in the super-gravity environment, the interphase mass transfer rate is 1-3 orders of magnitude higher than that in the traditional tower, so we can replace the huge chemical tower equipment as high as tens of meters with the super-gravity machine less than a few meters high. Therefore, the super-gravity engineering technology is considered to be a breakthrough technology to strengthen the transfer and multiphase reaction process, known as a cross-century technology, and the super-gravity machine is also known as the "transistor of the chemical industry."

ZZ-PRO硫磺回收技術(shù)

  隨著工業(yè)化進(jìn)程的不斷發(fā)展,煉油企業(yè)規(guī)模持續(xù)增大,尾氣處理規(guī)模也同比增加。BLUER-PRO工藝傳統(tǒng)的氣液吸收反應(yīng)器傳質(zhì)效率低,在一定的設(shè)計(jì)范圍內(nèi),隨著氣體流量的增大塔徑也不斷加大,造成了設(shè)備投資大,運(yùn)行成本高等問(wèn)題。

  采用超重力反應(yīng)器取代傳統(tǒng)鼓泡反應(yīng)器,極大強(qiáng)化了過(guò)程傳質(zhì)效率,增加了BLUER-PRO工藝對(duì)酸性氣的處理范圍,同時(shí)縮短氧化脫硫和催化劑再生時(shí)間,大大的減小設(shè)備尺寸,降低投資費(fèi)用。如處理7000m3/h的尾氣,使用超重力反應(yīng)器后,反應(yīng)器直徑只有2m左右,下圖為ZZ-PRO超重力系統(tǒng)的一個(gè)流程簡(jiǎn)圖。

流程ZZ-PRO工藝的原理

ZZ-PRO的基本反應(yīng)過(guò)程可以分為吸收與再生兩個(gè)階段

ZZ-PRO sulfur recovery technology

 

With the continuous development of industrialization, the scale of oil refining enterprises continues to increase, and the scale of exhaust gas treatment also increases year-on-year. The mass transfer efficiency of the traditional gas-liquid absorption reactor in BLUER-PRO process is low, and the tower diameter keeps increasing with the increase of gas flow rate within a certain design range, resulting in large equipment investment and high operating costs.

 

The use of super-gravity reactor to replace the traditional bubble reactor greatly strengthens the mass transfer efficiency of the process, increases the treatment range of acidic gas in the BLUER-PRO process, reduces the time of oxidation desulfurization and catalyst regeneration, greatly reduces the equipment size and investment costs. For example, when the exhaust gas of 7000m3/h is processed, the diameter of the reactor is only about 2m after the use of the super-gravity reactor. The following is a schematic diagram of the process of the ZZ-PRO super-gravity system.

Process Principle of ZZ-PRO process

The basic reaction process of ZZ-PRO can be divided into two stages: absorption and regeneration

吸收反應(yīng):

Absorption reaction:

H2S(氣體)+2Fe3+→2H++S°+2Fe2+

再生反應(yīng):

Regeneration reaction:

1/2 O2(氣體)+H2O+2Fe2+→2OH-+2Fe3+

總反應(yīng):

Total Response:

H2S+1/2O2→H2O+S°

  這一反應(yīng)發(fā)生于水基溶液中,所用水基溶液中的金屬離子能夠清除硫化物離子(S2-)的電子(負(fù)電荷),使之轉(zhuǎn)變成元素硫。此外,在再生過(guò)程中,該金屬能夠?qū)⒎@的電子轉(zhuǎn)移給氧(O2),使自己重新恢復(fù)到原來(lái)的金屬離子狀態(tài)。雖然具備這種功能的金屬有許多種,但是ZZ-PRO處理工藝技術(shù)選擇了鐵(Fe),因?yàn)殍F無(wú)毒而且活性好,轉(zhuǎn)化效率高。

This reaction takes place in an aqueous solution, where metal ions are used to remove electrons (negative charge) from the sulfide ion (S2 -) and convert it to elemental sulfur. In addition, during the regeneration process, the metal is able to transfer the trapped electrons to oxygen (O2) , restoring itself to the original metal ion state. Although there are many metals with this function, the ZZ-PRO treatment process technology chooses iron (Fe) because it is non-toxic and active, and the conversion efficiency is high.

 

Z-PRO工藝的特點(diǎn)

ZZ-PRO工藝不僅保留了BLUER-PRO工藝的所有優(yōu)點(diǎn),同時(shí),由于有革命性質(zhì)的改進(jìn),該工藝還存在以下優(yōu)點(diǎn):

(1)處理能力大,單套系統(tǒng)可處理上萬(wàn)立方米含硫化氫酸氣。

(2)設(shè)備體積小,處理同樣規(guī)模的尾氣設(shè)備體積是同類(lèi)工藝的2%左右。

(3)壓降低,該工藝可控制系統(tǒng)壓降在2kPa以下,而鼓泡式BLUER-PRO至少需要40kPa的壓降。

(4)設(shè)備投資少,為同類(lèi)工藝設(shè)備投資額的一半以下。

(5)反應(yīng)效率極高,相對(duì)同類(lèi)工藝有數(shù)量級(jí)的提升。

(6)不怕振動(dòng)和傾斜。

(7)開(kāi)停車(chē)容易,可在幾分鐘內(nèi)達(dá)到穩(wěn)定操作等。

Characteristics of the ZZ-PRO process

The ZZ-PRO process not only retains all the advantages of the BLUER-PRO process but also has the following advantages due to revolutionary improvements:

(1) Large processing capacity, a single set of systems can handle tens of thousands of cubic meters of hydrogen sulfide gas.

(2) The volume of the equipment is small, and the volume of the exhaust equipment dealing with the same scale is about 2% of the similar process.

(3) Pressure reduction, the process can control the system pressure drop below 2kPa, and the bubbling BLUER-PRO requires at least a 40kPa pressure drop.

(4) Less investment in equipment, less than half of the investment in similar process equipment.

(5) The reaction efficiency is extremely high, which is an order of magnitude improvement compared with similar processes.

(6) Not afraid of vibration and tilt.

(7) Easy to start and stop, and stable operation can be achieved in a few minutes.

適用范圍

  ZZ-PRO硫化氫氣體處理工藝廣泛應(yīng)用于石油提煉、天然氣開(kāi)采、地?zé)釟怏w發(fā)電、生物氣處理、垃圾填埋沼氣處理、飲料業(yè)二氧化碳?xì)怏w生產(chǎn)、潤(rùn)滑油生產(chǎn)等行業(yè)。對(duì)生產(chǎn)過(guò)程中產(chǎn)生的含硫化氫氣體幾乎可以完全回收,達(dá)到真正意義上的節(jié)能減排效果。

  在這些工業(yè)生產(chǎn)中,需處理的氣體流量從幾個(gè)立方米每小時(shí)到上萬(wàn)個(gè)立方米每小時(shí),氣體H2S濃度從100ppm到100%,氣壓從50KPa到4.5MPa,每天產(chǎn)生的硫從0.2噸到20多噸。

ZZ-PRO hydrogen sulfide gas treatment process is widely used in oil refining, natural gas exploitation, geothermal gas power generation, biogas treatment, landfill biogas treatment, beverage industry carbon dioxide gas production, lubricant production, and other industries. The hydrogen sulfide gas produced in the production process can be almost completely recovered, to achieve the real sense of energy saving and emission reduction effect.

 

In this industrial production, the gas flow to be treated ranges from a few cubic meters per hour to tens of thousands of cubic meters per hour, the gas H2S concentration ranges from 100ppm to 100%, the air pressure ranges from 50KPa to 4.5MPa, and the sulfur produced per day ranges from 0.2 tons to more than 20 tons.