## Introduction

MTP catalysts were formed by a ZSM-5 molecular sieve. The ZSM-5 molecular sieve has a unique pore structure that provides good ion exchange performance and shape selection selectivity1,2. Because of its good thermal stability, hydrothermal stability, wide distribution of Si/Al, and wide range of acid adjustability, ZSM-5 zeolite is a good solid acid catalyst and catalyst carrier3,4. It is widely used in the field of catalysis, such as in the petrochemical industry and coal chemical industry, as well as in the field of sewage purification and selective adsorption5,6.

Industrial wastewater contains many pollutants, among which organic compounds are one of the most toxic pollutants7,8. Zeolites are widely used for heavy metal ion removal9,10,11,12. It is necessary to have hydrophobic and oil-friendly adsorption of organic matter13. It is also important to improve the hydrophobicity of ZSM-5 by increasing the ratio of silicon to aluminum. However, the surface of ZSM-5 zeolite contains Si(Al)OH, which affects its hydrophobicity14. Generally, the static water contact angle (θ) is small and far from those of hydrophobic (θ > 90°) and superhydrophobic (θ > 150°) zeolites. This limits the partial application of ZSM-5 in hydrophobic catalysts and as a selective adsorbent. Modification of surfactant is an effective way to improve the hydrophobicity of a molecular sieve15,16. The hydrophobic group can be grafted onto the surface of the molecular sieve through the reaction of organosilane reagent with hydroxyl group. This improves its hydrophobicity and hydrophobic retention ability15.

Many published studies have reported that catalysts suitable for methanol to propylene (MTP) require small grain HZSM-5 molecular sieves with a high Si to Al ratio and a multistage pore composite structure14,17,18. Researchers have focused on the design and development of new MTP catalysts but rarely studied the comprehensive utilization technology of the functionalization of spent MTP catalysts. The spent MTP catalyst has a large specific surface area, high porosity, and good adsorption performance. There are several silicon aluminum hydroxyl groups on the surface, which have certain hydrophilicity and limit its application in oil-bearing wastewater. The process water, produced in the process of synthetic gas to oil or low carbon olefin from coal, is oily, and the COD content is high. It is necessary to pass the complicated oil–water separation process in the recycling process to ensure effective reuse of process water. Adsorption technology is often used in industrial plants to treat oil-bearing wastewater7,19. The selection and application of adsorbents is critical. In this paper, a spent MTP catalyst was modified with surface silane after acid–base treatment, and a superhydrophobic zeolite was obtained.

## Raw materials and preparation methods

### Raw materials

The raw materials were waste catalyst for methanol to propylene (sample: FMTP catalyst) in a fixed bed reactor, oxalic acid (H2C2O4), NaOH, HNO3 solution (68 wt%), OTS, deionized water, p-xylene, and n-hexane. The waste water is from the bottom of methanol recovery tower in Ningxia Coal Industry Co., Ltd. The detail composition for the waste water is depicted in Supplementary Figs. S1S12.

First, 100 g of spent MTP catalyst powder (below 200 mesh) was added into H2C2O4 solution (4 mol/L) with continuously stirring, and heated at 95 °C for 4–6 h in a water bath. Next, the solution was centrifuged (5000 r/min, 3 min), washed with deionized water, and dried at 120 °C overnight in a blower drying box (sample: FMTP-4 mol/LH2C2O4). Then, an acid-treated sample was added to 0.2 mol/L NaOH solution (liquid to solid ratio 5:1). Mechanical stirring treatment was conducted at 95 °C for 2 h, followed by centrifuging for 3 min at the rate of 5000 r/min. The obtained upper waste catalyst mud was then redispersed in 250 mL of dilute HNO3 solution (1 mol/L) and stirred magnetically for 30 min to remove the residue. After washing with deionized water until neutral, the catalyst was dried at 120 °C overnight in a blower drying box and calcined at 600 °C for 6 h in a muffle furnace. The powder was pressed into pieces and screened to obtain a 14–30 mesh. Then the adsorbent product can be obtained after acid–base treatment (sample: FMTP-4 mol/L H2C2O4 + 0.2 mol/L NaOH).

40 g of adsorbent product was added to 80 mL of OTS reagent and placed in a 500 mL crystallization kettle. The reaction was performed at 120 °C for 10 h. After cooling, centrifugation was carried out, and the adsorbent was washed with absolute methanol 4–6 times. Vacuum drying was then conducted overnight at 70 °C to obtain a hydrophobic adsorbent (sample: Adsorbent product). The detailed flow chart of material modification is shown in Fig. 1.

### Analysis and characterization methods

The crystal structure of the samples was analyzed by X-ray diffraction (XRD, X-pert3 powder diffractometer, Panaco, Netherlands) with Cu Kα radiation (λ = 0.15406 nm) at a tube voltage of 40 kV and a current of 40 mA. The sample was recorded at a scanning rate of 5° min−1 over the 2θ range of 5°–80°. The framework structure of the samples was analyzed by Fourier infrared spectrometry (FTIR, a Bruker V70, Germany). The samples were prepared by mixing 1 mg of sample (1 wt%) with 99 mg of optical spectra grade KBr (99 wt%) in the wavelength range of 500–4000 cm−1, with a resolution of 4 cm−1. The Brunauer–Emmet–Teller (BET) specific surface area and pore properties of the samples were analyzed by a physical adsorption instrument (ASAP2020 surface analyzer, the United States). The samples were pretreated at 350 °C for 8 h before measurement. BET formula was used to calculate the specific surface area, DFT method was used to plot the pore size distribution curve, BJH method was used to calculate the mesoporous distribution, and T-plot method was used to calculate the pore volume. The chemical states and surface element contents of samples were investigated using X-ray photoelectron spectrometer (XPS, Thermo ESCALAB 250xi, United States) with Al Kα radiation. The composition of the samples was recorded via X-ray fluorescence spectroscopy (XRF, Bruker S8 tiger type, Zeiss Merlin, Germany). The micromorphology of the samples was observed using scanning electron microscope (SEM, Carl Zeiss, Germany), and the chemical environment of 27Al and 29Si elements in the samples was studied by nuclear magnetic resonance (NMR, electronic JNM ECZ600r NMR, Japan). Potassium dichromate method was utilized to measure the COD content through a COD analyzer (Hash, USA), and the hydrophilic/phobic properties was evaluated by measuring static water contact angle employing an OSA-100 contact angle goniometer (Rhoda Germany). Liquid chromatography–mass spectrometry technology (LC–MS, Clarus SQ8T, Perkin Elmer LTD) was utilized to analyze the composition of waste water. Temperature programmed GC Column: the initial temperature at 40 °C for 3 min, a processing temperature at 230 °C for 5 min at the rate of 10 °C/min. Carrier gas (constant current mode) at a flow rate of 1 mL/min. MS setting conditions: filament current of 10 mA, EI MASS spectrum, ion source temperature at 250 °C, solvent delay 2 min, ion scanning range of 40–500 m/z.

Different weights of adsorbent (2 g, 4 g, 6 g, 8 g, and 10 g) and 100 mL of effluent containing different concentrations of COD (457.876 mg/L, 915.751 mg/L, 1831.503 mg/L, 3663.005 mg/L, 7326.01 mg/L and 12,210.017 mg/L) were added into a series of 250 mL iodine flasks. The wastewater mainly contained n-hexane, p-xylene, and methanol et al. After adjusting the pH, the effluent was placed at different temperatures (25 °C, 35 °C, 45 °C, 55 °C, and 65 °C) and oscillated for a certain time (30 min, 60 min, 90 min, 120 min, 180 min, 240 min, 270 min, and 300 min) in an oscillator to achieve adsorption equilibrium. Notably, when the adsorption rate and COD concentration were constant, the adsorption equilibrium was achieved. Finally, the COD concentration of wastewater was determined using the COD analyzer.

### Regeneration performance

The used hydrophobic adsorbent was calcined at 250 °C in a muffle furnace for 60 min to remove the adsorbed organic matter. After cooling down to room temperature, the obtained regenerated adsorbent can be reused in the wastewater for the removal of COD.

Herein, the popular Lagergren equations, including Pseudo first-order and second-order, as well as the Elovich model have been used to analyze the experiment data, identifying the mechanism of COD removal by modified FMTP adsorbent. The detail equations are described as follows.

#### Pseudo first-order model

$${\text{lg}}\left( {{\text{q}}_{{{\rm e}}} - {\text{q}}_{{{\rm t}}} } \right) = {\text{lgq}}_{{{\rm e}}} - {\text{K}}_{{1}} {{\rm t}}$$
(1)

where K1 is the first-order adsorption kinetic constant (min−1), qe is the adsorption amount in equilibrium (mg/g), and qt is the adsorption amount at time t (mg/g).

#### Pseudo second-order model10

$$\frac{{\text{t}}}{{{\text{q}}_{{{\rm e}}} }} = \frac{{1}}{{{\text{K}}_{{2}} {\text{q}}_{{{\rm e}}}^{{2}} }} + \frac{{1}}{{{\text{q}}_{{{\rm e}}} }}{\text{t}}$$
(2)

where K2 is the quasi-second-rate constant of adsorption (min−1) and qe is the adsorption amount (mg/g) in equilibrium.

#### Elovich model

$${\text{q}} = \frac{{1}}{{\text{b}}}{{\ln}}\left( {{\text{ab}}} \right) + \frac{{1}}{{\text{b}}}{\text{lnt}}$$
(3)

where a is the initial adsorption rate and 1/b is a parameter related to the number of adsorption sites.

#### Freundlich isotherms9,20

$${\text{Inq}}_{{{\rm e}}} = {\text{InK}}_{{{\rm f}}} + \frac{{1}}{{\text{n}}}{\text{InC}}_{{{\rm e}}}$$
(4)

where qe is the adsorption content of COD per unit adsorbent (mg/g) in equilibrium; Ce is the equilibrium concentration of COD in the solution (mg/L); Kf is the Freundlich isothermal constant (mg/g); and n is the adsorption strength (g/L).

#### Langmuir isotherms9,20

$$\frac{{1}}{{{\text{q}}_{{{\rm e}}} }} = \frac{{1}}{{{\text{q}}_{{{\rm m}}} }} + \frac{{1}}{{{\text{q}}_{{{\rm m}}} {\text{ K}}_{{{\rm l}}} {\text{ C}}_{{{\rm e}}} }}$$
(5)

where qm is the maximum adsorption capacity (mg/g) and Kl is the Langmuir constant.

$${\text{Inq}}_{{{\rm e}}} = {\text{ Inq}}_{{{\rm m}}} - \upbeta \upvarepsilon ^{{2}}$$
(6)

where β is a constant related to the adsorption energy, and the ε value can be obtained from the following formula:

$$\upvarepsilon = {\text{RT In}}\left( {{1} + \frac{{1}}{{{\text{C}}_{{{\rm e}}} }}} \right)$$
(7)

where R is the gas constant (8.314 J/mol·K) and T is the absolute temperature (K).

$$\Delta {\text{G}} = \Delta {\text{H}} - {\text{T}}\Delta {\text{S}}$$
(8)
$${\text{lg}}\left( {\frac{{{\text{q}}_{{{\rm e}}} }}{{{\text{C}}_{{{\rm e}}} }}} \right) = \frac{{\Delta {\text{S}}}}{{{2}{\text{.303R}}}} - \frac{{\Delta {\text{H}}}}{{{2}{\text{.303R}}}} \times \frac{{1}}{{\text{T}}}$$
(9)

In Eq. (9), qe is the solid equilibrium concentration (mg/L) and Ce is the solution equilibrium concentration (mg/L). ΔS and ΔH in Eq. (8) are calculated by the slope and intercept of the Van’t Hoff isothermal formula.

## Results and discussion

The XRD pattern of the adsorbent product is shown in Fig. 2a. The hydrophobic adsorbent product maintains a typical ZSM-5 molecular sieve structure, and the corresponding characteristic peaks corresponding to (011), (020), (051) and (033) crystal planes of ZSM-5 appear at 2θ = 7.9°, 8.8°, 23.1°, and 23.8°, respectively, indicating that the adsorbent channel has a long-range order22,23,24. It can be seen from Fig. 2b that the signals of C, Si, Al, and O elements in the samples before and after modification can be detected. The C 1s peak can be indexed to the air defiled carbon adsorbed on the surface of spent MTP catalyst, and all the samples show characteristic peaks of polluted carbon.

After modification with silane, the carbon content on the sample surface rises to 30.93%, which is attributed to the organic silane layer formed on the adsorbent surface. After the etching depth of the sample surface was extended from 10 to 50 nm, the carbon content decreases from 21.7 to 16.45%, demonstrating that the –Si(CH2)7CH3 group is successfully grafted onto the sample. The proposed surface reaction mechanism is as follows:

$${\text{Spent ZSM-5}} + {\text{H}}_{2} {\text{C}}_{2} {\text{O}}_{4} \to {\text{spent ZSM-5-H}} + {\text{C}}_{2} {\text{O}}_{4}^{2 - }$$
(10)
$${\text{Spent ZSM-5-H}} + {\text{NaOH}} \to {\text{spent ZSM-5-OH}} + {\text{H}}_{2} {\text{O}} + {\text{Na}}^{ + }$$
(11)
$${\text{Spent ZSM-5-OH}} + {\text{HNO}}_{3} \to {\text{ZSM-5}} + {\text{H}}_{2} {\text{O}} + {\text{NO}}_{3}^{ - }$$
(12)
$${\text{ZSM-5}} + {\text{OTS}} \to {\text{ZSM-5}} - {\text{Si}}({\text{CH}}_{2} )_{7} {\text{CH}}_{3}$$
(13)

Figure 2c shows the 27Al MAS NMR spectrum of the hydrophobic adsorbent product. Two kinds of aluminum species can be observed in the spent MTP catalyst. The peak at the general chemical displacement, δ = 50–60 ppm, belongs to the Al atom in the molecular sieve skeleton, which is tetrahedrally coordinated. The peak near δ = 0 is usually attributed to the hexahedral nonskeletal aluminum signal. There is a shoulder peak at δ = 47.8, which represents the signal of skeleton aluminum distributed on the outer surface of the molecular sieve or in a large hole. After modification of silane, the peak intensity of δ = 5.0 and δ = 58.0 increased, and the shoulder peak signal at δ = 47.8 disappeared, indicating that the –Si(CH2)7CH3 group has been grafted onto the hydrophobic adsorbent samples. And some pore space can be occupied, which was consistent with the BET results.

Figure 2d shows the static CA between the sample and water after silane modification. After OTS modification, the CA in Fig. 2d(1) reached 0° without water droplets, and when water dropped, the CA reached 159.1° [in Fig. 2d(2)], which shows a superhydrophobic state. It can be surmised that the surface of the sample is grafted with the low surface energy group –Si(CH2)7CH3, and the carbon chains are staggered to form a nanoscale rough surface, which improves the hydrophobicity of the sample surface. When p-xylene and n-hexane are dropped on the surface of the sample in Fig. 2d(3) and d(4), the droplets are immediately inhaled into the sample, indicating that the modified samples have strong adsorption to p-xylene and n-hexane.

Figure 2e and f shows the infrared spectrum of the adsorbent products. The ZSM-5 skeleton peak shows no obvious change after OTS modification, indicating that the skeleton structure of the adsorbent remains unchanged25. Absorption peaks at 1107 cm−1 and 804 cm−1 belong to the asymmetric expansion vibration peaks in the silicon oxygen tetrahedron, and the 457 cm−1 absorption peak indicates the Si–O–Si bending vibration. The absorption peak at 1230 cm−1 belongs to the asymmetric expansion vibration peak of silicon oxygen tetrahedron and aluminum oxygen tetrahedron in the ZSM-5 framework10. The absorption peaks of –CH3 and –CH2 appeared at 2859 cm−1, 2928 cm−1, and 2960 cm−1, respectively. This shows that the modified groups of –CH3 and –CH2 replace the Si–OH and –Si(CH2)7CH3 groups in the ZSM-5 skeleton and improve the hydrophobicity of the adsorbent.

The N2 adsorption and desorption curve and pore size distribution curve of the adsorbent products are shown in Fig. S1 (ESI). The adsorption capacity increased sharply when p/p0 < 0.05, indicating that there was microporous structure. The hysteresis ring appeared in the sample when p/p0 < 0.5, showing a characteristic type IV adsorption and desorption curve, indicating that the adsorbent product is a mesoporous composite material. Specific surface area and pore size analysis of the absorbent products are shown in Table 1. The specific surface area, pore volume, and pore size of the adsorbent after modification all decreased, suggesting that silane group grafting in the ZSM-5 molecular sieve pore occupies part of the inner space of the pore.

As shown in Fig. 3, the MTP catalyst sample after acid treatment shows an irregular ellipsoid shape with a uniform grain size of approximately 1.1 μm. After alkali treatment, the surface of the spheres became rough (Fig. 3c). However, the grain size for silane modified samples remained unchanged, and small aggregated particles appeared on the surface (Fig. 3d), testifying that the surface of the sample was loaded with silane groups.

As shown in Table 2, the ratio of Si/Al increases significantly after acid–base modification due to the increasing content of Si and decreasing content of Al element, which is similar to the Si/Al ratio in fresh catalysts. While the Si/Al ratio was almost unchanged after silane modification, certifying the composition of the adsorbent products was not affected by the silane modification. During the treatment of catalysts with different reagents, the elemental composition, except for Si and Al elements, show negligible change.

Particularly, the COD removal rate increases (in Fig. 4) gradually with the increasing dosage of adsorbent, which might be due to the large specific surface area. On the contrary, the content of adsorbed COD per gram of adsorbent shows a significant reduction with increasing adsorbent concentration. When the mass of adsorbent increased to 6 g, the COD adsorption capacity reached 156.3 mg and removal rate remained stable, suggesting the adsorption site reached saturation. Therefore, it can be determined that the optimum amount of adsorbent is 6 g, and the maximum removal rate of COD is 44.4%.